CN102844886A

CN102844886A - Use of indanthrene compounds in organic photovoltaics

Info

Publication number: CN102844886A
Application number: CN2011800196312A
Authority: CN
Inventors: M·克内曼; R·赫; J·H·黄; C·多尔; 曲建强; G·韦伯; G·麦特恩; P·埃尔克
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2010-02-19
Filing date: 2011-02-18
Publication date: 2012-12-26
Also published as: WO2011101810A1; AU2011216899B2; ZA201206949B; EP2537186A1; JP2013520791A; KR20130004907A; AU2011216899A1; EP2537186A4

Abstract

Disclosed is an organic solar cell which comprises at least one photoactive region which comprises at least one indanthrene compound which is in contact with at least one fullerene compound, and the use of indanthrene compounds in organic photovoltaics, especially in the form of a component cell of a tandem cell.

Description

The purposes of indanthrene compound in organic photovoltaic devices

Subject matter

The present invention relates to a kind of organic solar batteries that comprises at least one photosensitive area; Said photosensitive area comprises the indanthrene compound that at least a and at least a fullerene compound contacts, and also relates to the purposes of indanthrene compound in organic photovoltaic devices.

Technical background

Because fossil feedstock reduces and formed and as the CO of greenhouse gas in these raw materials of burning ₂, directly bringing into play the effect that becomes more and more important by the sunlight produce power." photovoltaic " is interpreted as meaning with radiant energy, mainly is that solar energy is converted into electric energy.

Compare with inorganic solar cell, light is not in organic solar batteries, directly to produce free carrier, but at first forms exciton, promptly is the electric neutrality excitation state of electronics-hole matching form.These excitons only can be through very high electric field or in suitable separation at the interface.In organic solar batteries, can not obtain sufficiently high electric field, therefore all be based on the exciton dissociation that photosensitive interface (organic donor-receiver interface or with the interface of inorganic semiconductor) is located about all existing ideas of organic solar batteries.For this reason, necessary is that the exciton that in the organic material volume, produces can diffuse to this photosensitive interface.Therefore, exciton diffuses to active interface and in organic solar batteries, plays key effect.In order to help photoelectric current, the exciton diffusion length in the good organic solar batteries must be in the order of magnitude scope of common transmission depth of light at least, thereby can utilize the major part of light.The efficient of organic solar batteries is through its open circuit voltage V _OCCharacterize.Other key properties are short circuit current I _SC, fill factor, curve factor FF and gained efficiency eta.

Have first kind of organic solar batteries being in the efficient in the percentage range and described (CW.Tang etc., Appl.Phys.Lett.48,183 (1986)) by Tang etc. in 1986.It is by having as the CuPc (CuPc) of donor material (p N-type semiconductor N) with as the perylene-3 of acceptor material (n N-type semiconductor N), 4:9, and two coating systems of the two imidazoles (PTCBI) of 10-tetracarboxylic acid constitute.

The current goal of organic photovoltaic devices provides solar cell of new generation, and it is obviously than the solar cell that is made up of silicon or other inorganic semiconductors such as cadmium indium selenides or cadmium telluride cheapness more.For this reason, also need suitable optical semiconductor absorbent material in addition.A kind of mode that absorbs a large amount of light and acquisition good efficiencies is to use the complementary semi-conducting material of a pair of light absorption, for example comprises shortwave absorbability n N-type semiconductor N and long wave absorbability p N-type semiconductor N.This notion is also based on above-mentioned first kind of organic solar batteries, so-called Tang battery.Although many fullerene compounds are absorbing light faintly only, yet found when with fullerene or fullerene derivate (like C60 or C72) during as the n N-type semiconductor N, can prepare effective solar cell.In addition, also known when using weak absorbability semi-conducting material, one of two solar cells can be placed another top and make up.At this moment, battery comprises the combination of weak absorbability semiconductor and the semiconductor (it absorbs shortwave radiation) complementary with it, and another battery comprise weak absorbability semiconductor and with the wherein combination of the semiconductor (it absorbs long-wave radiation) of complementation.With regard to regard to this laminated cell of fullerene or fullerene derivate combination, need two kinds of suitable p N-type semiconductor Ns, wherein a kind of absorption shortwave radiation and a kind of absorption long-wave radiation.The discovery of suitable semiconductor combination is not unessential.In laminated cell, the open circuit voltage Voc of each assembly stack.Total current receives the restriction of the assembly battery with lowest short-circuit current Isc.Therefore, two of each battery kinds of semi-conducting materials must accurately be adjusted each other.Therefore, be starved of p N-type semiconductor N organic absorbent material and be used for having high open circuit voltage and the organic solar batteries that can accept short circuit current, in laminated cell to make up with fullerene or fullerene derivate with long wave absorption.

Bohn (BASF) has synthesized first kind of indanthrene dyes in 1901, indanthrene blue RS, and it is first kind of representative of anthraquinone vat dyestuffs.Indanthrene is also referred to as indanthrone or C.I. pigment blue 60.

JP5102506A has described a kind of photovoltaic cell with photosensitive area, and the layer that comprises organic donor material is contacted with the layer that comprises organic acceptor material.Said photosensitive area comprises at least a indanthrene dyes and/or anthraquinone acridine ketone dyes, yet it is as just electron acceptor (n N-type semiconductor N, electrical conductivity body).Described suitable indanthrene dyes is the dyestuff of general formula (A):

Wherein

M and the n 0-4 that respectively does for oneself,

R ¹And R ²Respectively do for oneself halogen, alkyl, alkoxyl, hydroxyl, amino, acetyl group, carboxyl, nitro or cyanic acid, and

R ³And R ⁴The hydrogen or alkyl of respectively doing for oneself.

Suitable organic electronic donor described in the document is various phthalocyanines and the polymer with conjugated pi-system, for example polyacetylene.

Have surprisingly been found that at present the indanthrene compound advantageously is suitable for as the electron donor in the organic photovoltaic devices (p N-type semiconductor N, hole-conductive body).They be particularly suited for as the combination of at least a fullerene compound (like C60) of electron acceptor (n N-type semiconductor N, electrical conductivity body).Especially found that the indanthrene compound is applicable in the laminated cell, this is because it has the long wave absorbability and when making up with fullerene compound such as C60, demonstrates high open circuit voltage.

The invention summary

The present invention at first provides a kind of organic solar batteries that comprises at least one photosensitive area; Said photosensitive area comprises the indanthrene compound that at least a and at least a fullerene compound contacts, and wherein said indanthrene compound is selected from the compound of general formula (I):

Wherein

R ^aAnd R ^bBe selected from hydrogen, deuterium independently of one another, do not replace or substituted alkyl, do not replace or substituted cycloalkyl and not replacing or substituted aryl,

R ¹-R ¹²Group is selected from hydrogen, halogen, nitro, cyanic acid, hydroxyl, carboxyl, carboxylic acidulants base, SO independently of one another ₃H, azochlorosulfonate acid compound base, Ne ^aE ^bBe selected from each case and do not replace or substituted alkyl, alkoxyl, alkylthio group, cycloalkyl, aryl, aryloxy group, arylthio, heteroaryl, heteroaryloxy, heteroarylthio, oligomeric (mixing) aryl, oligomeric (mixing) aryloxy group and oligomeric (mixing) alkylthio group, wherein E ^aAnd E ^bBe hydrogen, alkyl, cycloalkyl or aryl independently of one another.

The present invention further provides as above defined and hereinafter as the purposes of general formula (I) compound of the electron donor in the organic photovoltaic devices (p N-type semiconductor N, hole-conductive body).

The present invention further provides the new compound of formula I, i.e. R wherein ¹-R ¹²Be hydrogen and R ^aAnd R ^bThe two is the formula I compound of deuterium.

The present invention further provides the new compound of formula I, i.e. R wherein ¹And R ⁹The two is phenoxy group and R ^a, R ^b, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ¹⁰, R ¹¹And R ¹²Group is hydrogen, perhaps R ⁵And R ⁸The two is methoxyl group and R ^a, R ^b, R ¹, R ², R ³, R ⁴, R ⁶, R ⁷, R ⁹, R ¹⁰, R ¹¹And R ¹²Group is the formula I compound of hydrogen.

Brief description

Fig. 1 has shown the solar cell that is suitable for using the indanthrene compound and has positive interposed structure.

Fig. 2 has shown the solar cell with inverted structure.

Fig. 3 has shown the solar battery structure that has positive interposed structure and be the donor-receiver interface of body heterojunction form.

Fig. 4 has shown the solar battery structure that has inverted structure and be the donor-receiver interface of body heterojunction form.

Fig. 5 has shown the structure of laminated cell.

Fig. 6 has shown to have the solar battery structure at the donor-receiver interface of the body heterojunction form of configuration in gradient.

Fig. 7 has shown the absorption spectrum of the vapor-deposited film of indanthrene blue.

Fig. 8 has shown 4, the absorption spectrum of the vapor-deposited film of 4 '-dimethoxy indanthrone.

Fig. 9 has shown 5, the absorption spectrum of the vapor-deposited film of 5 '-two phenoxy group indanthrone.

Detailed Description Of The Invention

With regard to the present invention, the photosensitive heterojunction that wording " photosensitive area " expression is formed by at least a electronic conductivity organic material and at least a P-conductivity organic material.

With regard to the present invention, when since the light absorption at heterojunction place and separation of charge so the charge carrier (photo-generated carrier) of formation when in organic material, transmitting with the hole form, said material is called " P-conductivity ".Correspondingly, when photo-generated carrier transmitted in organic material with electronic form, said material was called " electronic conductivity ".

" heterojunction " is meant the interface zone between electronic conductivity material and the P-conductivity material.

" photosensitive heterojunction " is meant the heterojunction between electronic conductivity material and the P-conductivity material; The excitation state (" exciton ") that form owing to the light absorption in electronic conductivity material and/or the P-conductivity material this moment is separated into independent charge carrier (being electronics and hole) in heterojunction regions; Said then charge carrier transmits again through said electronic conductivity material and/or P-conductivity material; Reach electric contact, can take out electric energy at this electric contact place.

" planar heterojunction " is meant the heterojunction between electronic conductivity material and the P-conductivity material; Interface between said electronic conductivity material and the said P-conductivity material forms (referring to C.W.Tang as the combination interface between said two kinds of material areas (being a zone of said electronic conductivity material and a zone of said P-conductivity material) basically at this moment; Appl.Phys.Lett; 48 (2); 183-185 (1986) or N.Karl etc.; Mol.Cryst.Liq.Cryst; 252,243-258 (1994)).

" body heterojunction " is meant the heterojunction between electronic conductivity material and the P-conductivity material; This moment, said electronic conductivity material and said P-conductivity material were partially mixed at least each other; Thereby make interface between said electronic conductivity material and the said P-conductivity material comprise and a plurality ofly be distributed in interface fragment in the said material blends volume (referring to for example C.J.Brabec etc.; Adv.Funct.Mater.; 11 (1), 15 (2001)).

Use with hereinafter relevant term " indanthrene compound " and " indanthrone compound " synonym with the used indanthrene compound of the present invention here.

The used indanthrene compound of the present invention is the light-sensitive material that in long wavelength's scope of solar spectrum, has high absorption coefficient.They are particularly useful in the assembly battery of laminated cell, thereby obtain maximum optical yield and high voltage.Therefore, can further improve the efficient of organic solar batteries.

With regard to the present invention, wording " does not replace or substituted alkyl; alkoxyl; alkylthio group; cycloalkyl; aryl; aryloxy group; Arylthio; Heteroaryl; Heteroaryloxy; Heteroarylthio; Oligomeric (mixing) aryl; Oligomeric (mixing) aryloxy group and oligomeric (mixing) alkylthio group " expression do not replace or substituted alkyl; replace or substituted alkoxyl; replace or substituted alkylthio group; replace or substituted cycloalkyl; replace or substituted aryl; replace or substituted aryloxy group; Do not replace or substituted arylthio; Do not replace or substituted heteroaryl; Do not replace or substituted heteroaryloxy; Do not replace or substituted heteroarylthio; Do not replace or substituted oligomeric (mixing) aryl; Not replacement or substituted oligomeric (mixing) aryloxy group and not replacement or substituted oligomeric (mixing) arylthio.

With regard to the present invention, wording " alkyl " comprises the straight or branched alkyl.Alkyl is preferably C ₁-C ₃₀Alkyl especially is C ₁-C ₂₀Alkyl most preferably is C ₁-C ₁₂Alkyl.The instance of alkyl especially is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-hexadecyl, n-octadecane base and n-eicosane base.

Wording " alkyl " also comprise its carbochain can between be separated with one or more being selected from-O-,-S-,-NR ^c-,-C (=O)-,-S (=O)-and/or-S (=O) ₂-the alkyl of non-adjacent group.R ^cPreferred hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl.

Substituted alkyl depends on the length of alkyl chain, can have one or more (as 1,2,3,4,5 or above 5) substituting group.These substituting groups preferably are selected from cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, fluorine, chlorine, bromine, hydroxyl, sulfydryl, cyanic acid, nitro, nitroso, formoxyl, acyl group, COOH, carboxylic acidulants base, alkyl carbonyl oxy, carbamoyl, SO independently of one another ₃H, azochlorosulfonate acid compound base, sulfoamino-group, sulfoamido, amidino groups; NE ¹E ², E wherein ¹And E ²Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently of one another.The cycloalkyl of said alkyl, Heterocyclylalkyl, aryl and heteroaryl substituting group can be not replacement or substituted again; Suitable substituents is for hereinafter to the described substituting group of these groups.

Carboxylic acidulants and azochlorosulfonate acid compound are represented carboxylic acid functional and sulfonic acid functional group's derivative respectively, especially are metal carboxylate or sulfonate, carboxylate or sulfonate functionality or carboxylic acid amides or sulfonamide functional group.

The substituted alkyl of aryl (" aralkyl " hereinafter is also referred to as aryl alkyl) has at least one like defined replacement or substituted aryl hereinafter.Alkyl in " aralkyl " can have at least one other substituting group and/or be separated with one or more being selected from-O-,-S-,-NR ^d-,-C (=O)-,-S (=O)-and/or-S (=O) ₂-non-adjacent group.R ^dBe preferably hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl.Aralkyl is preferably phenyl-C ₁-C ₁₀Alkyl, more preferably phenyl-C ₁-C ₄Alkyl, for example benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl alcohol-1-base, 2-phenylpropyl alcohol-1-base, 3-phenylpropyl alcohol-1-base, 1-benzene fourth-1-base, 2-benzene fourth-1-base, 3-benzene fourth-1-base, 4-benzene fourth-1-base, 1-benzene fourth-2-base, 2-benzene fourth-2-base, 3-benzene fourth-2-base, 4-benzene fourth-2-base, 1-(benzyl) second-1-base, 1-benzyl-1-(methyl) second-1-base or 1-benzyl-1-(methyl) third-1-base; Preferred benzyl and 2-phenethyl.

The substituted alkyl of halogen (" haloalkyl ") comprises the straight or branched alkyl that at least one hydrogen atom wherein or all hydrogen atoms are replaced by halogen.Halogen atom is preferably selected from fluorine, chlorine and bromine, especially is selected from fluorine and bromine.The instance of haloalkyl especially is a chloromethyl; Bromomethyl; Dichloromethyl; Trichloromethyl; Methyl fluoride; Difluoromethyl; Trifluoromethyl; The chlorine methyl fluoride; Dichlorofluoromethyl; Chlorodifluoramethyl-; The 1-chloroethyl; The 1-bromoethyl; The 1-fluoro ethyl; The 2-fluoro ethyl; 2; 2-two fluoro ethyls; 2; 2; The 2-trifluoroethyl; 2-chloro-2-fluoro ethyl; 2-chloro-2; 2-two fluoro ethyls; 2; 2-two chloro-2-fluoro ethyls; 2; 2; 2-three chloroethyls; Pentafluoroethyl group; The 2-fluoropropyl; The 3-fluoropropyl; 2; 2-two fluoropropyls; 2; 3-two fluoropropyls; The 2-chloropropyl; The 3-chloropropyl; 2; 3-two chloropropyls; The 2-bromopropyl; The 3-bromopropyl; 3,3, the 3-trifluoro propyl; 3; 3,3-three chloropropyls;-CH ₂-C ₂F ₅,-CF ₂-C ₂F ₅,-CF (CF ₃) ₂, 1-methyl fluoride-2-fluoro ethyl, 1-chloromethyl-2-chloroethyl, 1-bromomethyl-2-bromoethyl, 4-fluorine butyl, 4-chlorobutyl, 4-brombutyl, nine fluorine butyl, 5-fluoro-1-amyl group, 5-chloro-1-amyl group, 5-bromo-1-amyl group, 5-iodo-1-amyl group, 5; 5; 5-three chloro-1-amyl groups, 11 fluorine amyl groups, 6-fluoro-1-hexyl, 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-1-hexyl, 6; 6,6-three chloro-1-hexyls or ten difluoro hexyls.

Above about not replacing or the description of substituted alkyl also is applicable to and does not replace or substituted alkoxyl, do not replace or substituted alkyl amino, do not replace or substituted alkylthio group etc.

With regard to the present invention, " cycloalkyl " is meant to have preferred 3-10, more preferably the alicyclic group of 5-8 carbon atom.The instance of cycloalkyl especially is cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl or ring octyl group.

Substituted cycloalkyl depends on that ring size can have one or more one or more (as 1,2,3,4,5 or above 5) substituting groups that have.These substituting groups preferably are selected from alkyl, alkoxyl, alkylthio group, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, fluorine, chlorine, bromine, hydroxyl, sulfydryl, cyanic acid, nitro, nitroso, formoxyl, acyl group, COOH, carboxylic acidulants base, alkyl carbonyl oxy, carbamoyl, SO independently of one another ₃H, azochlorosulfonate acid compound base, sulfoamino-group, sulfoamido, amidino groups; NE ³E ⁴, E wherein ³And E ⁴Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently of one another.Under substituted situation, said cycloalkyl preferably has one or more, like 1,2,3,4 or 5 C ₁-C ₆Alkyl.The instance of substituted cycloalkyl especially is 2-and 3-methylcyclopentyl; 2-and 3-ethyl cyclopenta; 2-; 3-and 4-methylcyclohexyl; 2-; 3-and 4-ethyl cyclohexyl; 2-; 3-and 4-propyl group cyclohexyl; 2-; 3-and 4-isopropylcyclohexyl-; 2-; 3-and 4-butyl cyclohexyl, 2-; 3-and 4-sec-butyl cyclohexyl, 2-; 3-and 4-tert-butylcyclohexyl; 2-; 3-and 4-methyl suberyl; 2-; 3-and 4-ethyl suberyl, 2-; 3-and 4-propyl group suberyl, 2-; 3-and 4-isopropyl suberyl; 2-; 3-and 4-butyl suberyl; 2-; 3-and 4-sec-butyl suberyl, 2-; 3-and 4-tert-butyl group suberyl, 2-; 3-; 4-and 5-methyl ring octyl group; 2-; 3-; 4-and 5-ethyl ring octyl group, 2-; 3-; 4-and 5-propyl group ring octyl group.

With regard to the present invention, wording " aryl " comprises having 6-18, and preferred 6-14 is individual, more preferably the monocycle of 6-10 carbon atom or polycyclic aromatic alkyl.Aryl groups, especially phenyl, naphthyl, indenyl, fluorenyl, anthryl, phenanthryl, and the four phenyl, , pyrenyl, etc., in particular phenyl or naphthyl.

Substituted aryl depends on that the quantity of its member ring systems and size can have one or more (as 1,2,3,4,5 or above 5) substituting group.These substituting groups preferably are selected from alkyl, alkoxyl, alkylthio group, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, fluorine, chlorine, bromine, hydroxyl, sulfydryl, cyanic acid, nitro, nitroso, formoxyl, acyl group, COOH, carboxylic acidulants base, alkyl carbonyl oxy, carbamoyl, SO independently of one another ₃H, azochlorosulfonate acid compound base, sulfoamino-group, sulfoamido, amidino groups; NE ⁵E ⁶, E wherein ⁵And E ⁶Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently of one another.Alkyl on the aryl, alkoxyl, alkyl amino, alkylthio group, cycloalkyl, Heterocyclylalkyl, aryl and heteroaryl substituting group can be not replacement or substituted again.As far as these groups, with reference to substituting group mentioned above.Substituting group on the aryl is preferably selected from alkyl, alkoxyl, haloalkyl, halogenated alkoxy, aryl, fluorine, chlorine, bromine, cyanic acid and nitro.Substituted aryl more preferably has 1,2,3,4 or 5 usually, preferred 1,2 or 3 substituent substituted-phenyl.

Substituted aryl is preferably by the substituted aryl of at least one alkyl (" alkaryl " hereinafter is also referred to as alkylaryl).Alkaryl depends on that the size of aromatic ring system can have one or more (as 1,2,3,4,5,6,7,8,9 or above 9) alkyl substituent.Alkyl substituent can be not replacement or substituted.Thus, with reference to above with do not replace the description relevant with substituted alkyl.In preferred embodiments, alkaryl only has the unsubstituted alkyl substituting group.Alkaryl is preferably has 1,2,3,4 or 5, and preferred 1,2 or 3, the more preferably phenyl of 1 or 2 alkyl substituent.

Aryl with one or more groups for example is 2-; 3-and 4-aminomethyl phenyl, 2,4-; 2,5-; 3; 5-and 2,6-3,5-dimethylphenyl, 2,4; The 6-trimethylphenyl, 2-; 3-and 4-ethylphenyl, 2,4-; 2; 5-; 3,5-and 2,6-diethyl phenyl, 2; 4,6-triethyl group phenyl, 2-; 3-and 4-propyl group phenyl, 2; 4-; 2,5-; 3,5-and 2,6-dipropyl phenyl; 2,4,6-tripropyl phenyl, 2-; 3-and 4-isopropyl phenyl; 2,4-; 2,5-; 3,5-and 2; The 6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl; 2-; 3-and 4-butyl phenyl, 2,4-; 2,5-; 3; 5-and 2,6-dibutyl phenyl, 2,4; 6-tributyl phenyl, 2-; 3-and 4-isobutyl phenenyl, 2; 4-; 2,5-; 3,5-and 2; 6-diisobutyl phenyl, 2,4; 6-triisobutyl phenyl, 2-; 3-and 4-secondary butyl phenenyl, 2; 4-; 2,5-; 3,5-and 2; 6-two secondary butyl phenenyls, 2,4; 6-three secondary butyl phenenyls, 2-; 3-and 4-tert-butyl-phenyl, 2; 4-; 2,5-; 3,5-and 2; 6-di-tert-butyl-phenyl and 2,4,6-tri-tert phenyl; 2-, 3-and 4-methoxyphenyl, 2,4-, 2,5-, 3,5-and 2; The 6-Dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3-and 4-ethoxyl phenenyl; 2,4-, 2,5-, 3,5-and 2,6-diethoxy phenyl; 2,4,6-triethoxy phenyl, 2-, 3-and 4-propoxyl group phenyl, 2; 4-, 2,5-, 3,5-and 2,6-dipropoxy phenyl, 2-, 3-and 4-isopropyl phenyl; 2,4-, 2,5-, 3,5-and 2,6-diisopropoxy phenyl and 2-, 3-and 4-butoxy phenyl; 2-, 3-and 4-cyano-phenyl.

Above about not replacing or the description of substituted aryl also is applicable to and does not replace or substituted aryloxy group and not replacement or substituted arylthio.The instance of aryloxy group is phenoxy group, naphthoxy or anthracene oxygen base.The instance of arylthio is thiophenyl, naphthalene sulfenyl or anthracene sulfenyl.

With regard to the present invention, wording " Heterocyclylalkyl " comprises having 5-8 annular atoms usually, the non-aromatics of preferred 5 or 6 annular atomses, unsaturated or complete saturated alicyclic group.Compare with corresponding cycloalkyl, in the Heterocyclylalkyl 1,2,3,4 or surpass 4 ring carbon atoms by hetero-atom or contain heteroatomic group and replace.Said hetero-atom or contain heteroatomic group and be preferably selected from-O-,-S-,-NR ^e-,-C (=O)-,-S (=O)-and/or-S (=O) ₂-.R ^eBe preferably hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl.Heterocyclylalkyl is unsubstituted or optional one or more as 1,2,3,4,5,6 or 7 identical or different group of having.These preferably are selected from alkyl, alkoxyl, alkyl amino, alkylthio group, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, fluorine, chlorine, bromine, hydroxyl, sulfydryl, cyanic acid, nitro, nitroso, formoxyl, acyl group, COOH, carboxylic acidulants base, alkyl carbonyl oxy, carbamoyl, SO independently of one another ₃H, azochlorosulfonate acid compound base, sulfoamino-group, sulfoamido, amidino groups; NE ⁵E ⁶, E wherein ⁵And E ⁶Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently of one another.Examples of heteroalkyl in particular pyrrolidinyl, piperidinyl, 2,2,6,6 - tetramethyl piperidinyl, imidazolidinyl, pyrazolidinyl,

yl alkyl, morpholinyl, thiazolidinyl , isothiazole alkyl, iso

oxazolidinyl, piperazinyl, tetrahydro-thienyl, dihydro-thiophene-2 - yl, tetrahydrofuranyl, dihydrofuran-2 - yl, tetrahydropyranyl, 1,2 -

azole -5 - yl, 1,3 -

yl-2 - group and two alkyl.

The substituted heterocycle alkyl depends on that ring size can have one or more (as 1,2,3,4,5 or above 5) substituting group.These preferably are selected from alkyl, alkoxyl, alkylthio group, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, fluorine, chlorine, bromine, hydroxyl, sulfydryl, cyanic acid, nitro, nitroso, formoxyl, acyl group, COOH, carboxylic acidulants base, alkyl carbonyl oxy, carbamoyl, SO independently of one another ₃H, azochlorosulfonate acid compound base, sulfoamino-group, sulfoamido, amidino groups; NE ⁷E ⁸, E ⁷And E ⁸Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently of one another.Under substituted situation, Heterocyclylalkyl preferably has one or more, like 1,2,3,4 or 5 C ₁-C ₆Alkyl.

With regard to the present invention, wording " heteroaryl " comprises monocycle or many cyclic groups of heteroaromatic.Except that ring carbon atom, these have 1,2,3,4 or surpass 4 ring hetero atoms.Said hetero-atom is preferably selected from oxygen, nitrogen, selenium and sulphur.Heteroaryl preferably has 5-18, like 5,6,8,9,10,11,12,13 or 14 annular atomses.

Monocyclic heteroaryl is preferably a 5 - or 6 - membered heteroaryl group, such as 2 - furyl group (furan-2 - yl) 3 - furyl group (furan-3 - yl), 2 - thienyl (thiophene-2- - yl) 3 - thienyl (thiophen-3 - yl), selenium thiophene -2 - yl, selenium Thiophene-3 - yl, 1H-pyrrol-2 - yl, 1H-pyrrol-3 - yl, pyrrol-1 - yl, imidazol-2 - yl, imidazol-1 - yl, imidazol-4 - yl, pyrazol-1 - yl, pyrazol-3 - yl, pyrazol-4 - yl, pyrazol-5 - yl, 3 - iso

yl group, a 4 - iso azole group, a 5 - iso

yl group, a 3 - isothiazolone 4 - isothiazolyl, 5 - isothiazolyl, 2 -

thiazolyl, 4 -

thiazolyl, 5 -

yl group, 2 - thiazolyl 4 - thiazolyl, 5 - thiazolyl, 1,2,4 -

oxadiazol-3 - yl, 1,2,4 -

oxadiazol-5 - yl, 1,3,4 - oxadiazol-2 - group, 1,2,4 - thiadiazol-3 - yl, 1,2,4 - thiadiazol -5 - yl, 1,3,4 - thiadiazol-2 - yl, 4H-[1,2,4] - triazol-3 - yl, 1,3,4 - triazol-2 - yl, 1,2,3 - triazol-1 - yl, 1,2,4 - triazol-1 - yl, pyridin-2 - yl, pyridin-3 - yl, pyridin-4 - yl, 3 - pyridazinyl group, 4 - pyridazinyl group, a 2 - pyrimidinyl group, a 4 - pyrimidinyl group, a 5 - pyrimidinyl, 2 - pyrazinyl, 1, 3,5 - triazin-2 - yl and 1,2,4 - triazin-3 - yl.

Polyheteroaromatic has 2,3,4 or surpass 4 fused rings.It is saturated or part is undersaturated that said fused rings can be aromatics.Polycyclic heteroaryl Examples of quinolyl, isoquinolyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, iso-benzofuranyl, benzothienyl, benzo azole base, benzisoxazolyl

thiazolyl, benzothiazolyl, benzothienyl oxadiazolyl; benzo thiadiazolyl, benzo

piperazinyl, benzo pyrazolyl, benzimidazolyl, benzotriazolyl, benzo triazinyl, benzoselenazole, thienyl, thienyl and thienyl, thienyl and pyrimidinyl, thiazolyl and benzothiazolyl, dibenzo-pyrrolyl group (carbazolyl), dibenzofuran group, dibenzothiophene group, naphthyl and [2,3-b] thienyl, naphtho [2,3-b] furanyl, dihydro-indolyl, dihydro-indolizinyl, dihydro-iso-indolyl, dihydro quinolinyl, dihydro- isoquinolyl.

Substituted heteroaryl depends on that the quantity of its member ring systems and size can have one or more (as 1,2,3,4,5 or above 5) substituting group.These preferably are selected from alkyl, alkoxyl, alkylthio group, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, fluorine, chlorine, bromine, hydroxyl, sulfydryl, cyanic acid, nitro, nitroso, formoxyl, acyl group, COOH, carboxylic acidulants base, alkyl carbonyl oxy, carbamoyl, SO independently of one another ₃H, azochlorosulfonate acid compound base, sulfoamino-group, sulfoamido, amidino groups; NE ⁹E ¹⁰, E wherein ⁹And E ¹⁰Be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently of one another.Halogenic substituent is preferably fluorine, chlorine or bromine.Said substituting group is preferably selected from C ₁-C ₆Alkyl, C ₁-C ₆Alkoxyl, hydroxyl, carboxyl, halogen and cyanic acid.

Above-mentioned about not replacing or the description of substituted heteroaryl also is applicable to and does not replace or substituted heteroaryloxy and not replacement or substituted heteroarylthio.

With regard to the present invention, wording " oligomeric (mixing) aryl " expression has the not replacement or the substituted group of at least two repetitives.Said repetitive can all have identical definition, some repetitives can have different definition or all repetitives can have different definition.Said repetitive is selected from arlydene, inferior heteroaryl and combination thereof.Said arlydene is the divalent group derived from aromatics, preferably derived from the divalent group of benzene or naphthalene, as 1; 2-phenylene (adjacent phenylene), 1,3-phenylene (metaphenylene), 1,4-phenylene (to phenylene), 1; 2-naphthylene, 2,3-naphthylene, 1,4-naphthylene etc.Said inferior heteroaryl is the divalent group derived from heteroaromatic, is preferably the divalent group derived from thiophene or furans.The end group of oligomeric (mixing) aryl is a monoradical.This is equally preferably derived from above-mentioned repetitive.Said oligomeric (mixing) aryl can be not replacement or substituted.Replace oligomeric (mixing) aryl and depend on that the quantity of its member ring systems and size can have one or more (as 1,2,3,4,5,6,7,8,9 or above 9) substituting group.These substituting groups preferably are selected from unsubstituted alkyl, haloalkyl, fluorine or chlorine independently of one another.

Suitable repetitive is as follows:

R wherein ^fGroup is alkyl, alkoxyl, haloalkyl, fluorine or chlorine independently of one another, and y is 0,1,2,3 or 4, and x is 0,1 or 2.

Preferred oligomeric aryl is xenyl, para-terpheny base, meta-terphenyl base, ortho-terphenyl base, tetrad phenyl (as to the tetrad phenyl), 5-linked phenyl (as to the 5-linked phenyl).

Preferred oligomeric heteroaryl is:

Wherein # representes the binding site with said molecule remainder, and

A is 1,2,3,4,5,6,7 or 8,

N is 1-12, preferred 1-6.

A is preferably 1 or 2.

C _nH _2n+1Group is preferably methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl or n-hexyl.

The instance of oligomeric heteroaryl is 2,2-bithiophene-5-base and 5 "-hexyl-2,2 "-bithiophene-5-base.

Halogen is represented fluorine, chlorine, bromine or iodine.The preferred fluorine or chlorine of halogen.

According to above-mentioned definition, above-mentioned formula (I) and the R described in the formula hereinafter ¹-R ¹²Base and R ^a-R ^bInstantiation be:

Methyl; Ethyl; N-pro-pyl; Isopropyl; Normal-butyl; Isobutyl group; Sec-butyl; The tert-butyl group; N-pentyl; N-hexyl; N-heptyl; N-octyl; N-nonyl; Positive decyl; The n-undecane base; Dodecyl; The n-tridecane base; The n-tetradecane base; N-hexadecyl; N-octadecane base and n-eicosane base; The 2-methoxy ethyl; The 2-ethoxyethyl group; 2-propoxyl group ethyl; The 2-butoxyethyl group; The 3-methoxy-propyl; The 3-ethoxycarbonyl propyl; 3-propoxyl group propyl group; 3-butoxy propyl group; 4-methoxyl group butyl; 4-ethyoxyl butyl; 4-propoxyl group butyl; 3; The 6-dioxaheptyl; 3; 6-dioxa octyl group; 4; 8-dioxa nonyl; 3; 7-dioxa octyl group; 3; 7-dioxa nonyl; 4; 7-dioxa octyl group; 4; 7-dioxa nonyl; 2-and 4-butoxy butyl; 4; 8-dioxa decyl; 3; 6; 9-trioxa decyl; 3; 6; 9-trioxa undecyl; 3; 6; 9-trioxa dodecyl; 3; 6; 9; 12-four oxa-tridecyls and 3; 6; 9,12-four oxa-myristyls;

2-methylmercaptoethyl; 2-ethylmercapto group ethyl; 2-rosickyite base ethyl; 2-butylthio ethyl; 3-methyl mercapto propyl group; The 3-ethylsuleenyl propyl; 3-rosickyite base propyl group; 3-butylthio propyl group; 4-methyl mercapto butyl; 4-ethylmercapto group butyl; 4-rosickyite Ji Dingji; 3; 6-dithia heptyl; 3; 6-dithia octyl group; 4,8-dithia nonyl; 3,7-dithia octyl group; 3; 7-dithia nonyl; 2-and 4-butylthio butyl; 4; 8-dithia decyl; 3,6,9-three thia decyls; 3; 6; 9-three thia undecyls; 3,6,9-three thia dodecyls; 3; 6; 9,12-four thia tridecyls and 3,6; 9,12-four thia myristyls;

The 2-monomethyl-and the single ethylamino ethyl of 2-; The 2-dimethyl aminoethyl; 2-and 3-dimethylaminopropyl; The single isopropyl aminopropyl of 3-; The amino butyl of the single propyl group of 2-and 4-; 2-and 4-dimethylamino butyl; 6-methyl-3,6-diaza heptyl; 3,6-dimethyl-3; 6-diaza heptyl; 3,6-diaza octyl group; 3,6-dimethyl-3; 6-diaza octyl group; 9-methyl-3,6,9-three azepine decyls; 3; 6,9-trimethyl-3,6; 9-three azepine decyls; 3; 6,9-three azepine undecyls; 3,6; 9-trimethyl-3; 6,9-three azepine undecyls; 12-methyl-3,6; 9; 12-four azepine tridecyls and 3,6,9; 12-tetramethyl-3; 6,9,12-four azepine tridecyls;

(1-ethyl ethylidene) amino ethylidene, (1-ethyl ethylidene) amino propylidene, (1-ethyl ethylidene) amino butylidene, (1-ethyl ethylidene) amino inferior decyl and (1-ethyl ethylidene) amino inferior dodecyl;

Propane-2-ketone-1-base, butane-3-ketone-1-base, butane-3-ketone-2-base and 2-ethylpentane-3-ketone-1-base;

2-methylsulfinyl ethyl, 2-ethyl sulfinyl ethyl, 2-propyl group sulfinyl ethyl, 2-isopropyl sulfinyl ethyl, 2-butyl sulfinyl ethyl, 2-and 3-methylsulfinyl propyl group, 2-and 3-ethyl sulfinyl propyl group, 2-and 3-propyl group sulfinyl propyl group, 2-and 3-butyl sulfinyl propyl group, 2-and 4-methylsulfinyl butyl, 2-and 4-ethyl sulfinyl butyl, 2-and 4-propyl group sulfinyl butyl and 4-butyl sulfinyl butyl;

2-methyl sulphonyl ethyl, 2-ethylsulfonyl ethyl, 2-sulfonyl propyl base ethyl, 2-isopropyl sulfonyl ethyl, 2-butyl sulfonyl ethyl, 2-and 3-methyl sulphonyl propyl group, 2-and 3-ethylsulfonyl propyl group, 2-and 3-sulfonyl propyl base propyl group, 2-and 3-butyl sulfonyl propyl group, 2-and 4-methyl sulphonyl butyl, 2-and 4-ethylsulfonyl butyl, 2-and 4-sulfonyl propyl Ji Dingji and 4-butyl sulfonyl butyl;

Carboxymethyl, 2-carboxyethyl, 3-carboxylic propyl group, 4-carboxylic butyl, 5-carboxylic amyl group, 6-carboxylic hexyl, 8-carboxylic octyl group, 10-carboxylic decyl, 12-carboxyl dodecyl and 14-carboxyl myristyl;

Sulphur methyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulphur butyl, 5-sulphur amyl group, 6-sulphur hexyl, 8-sulphur octyl group, 10-sulphur decyl, 12-sulphur dodecyl and 14-sulphur myristyl;

2-ethoxy, 2-and 3-hydroxypropyl, 3-and 4-hydroxyl butyl and 8-hydroxyl-4-oxa-octyl group;

2-cyano ethyl, 3-cyanic acid propyl group, 3-and 4-cyanic acid butyl;

The 2-chloroethyl, 2-and 3-chloropropyl, 2-, 3-and 4-chlorobutyl, 2-bromoethyl, 2-and 3-bromopropyl and 2-, 3-and 4-brombutyl;

2-nitro-ethyl, 2-and 3-nitro propyl group and 2-, 3-and 4-nitro butyl;

Methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy and own oxygen base;

Methyl mercapto, ethylmercapto group, rosickyite base, butylthio, penta sulfenyl and own sulfenyl;

Methylamino, ethylamino, third amino, fourth amino, penta amino, oneself amino, two encircle penta amino, dicyclohexylamine base, two ring amino in heptan, diphenyl amino and dibenzyl amino;

Formamido group, acetylamino, propionamido and benzamido;

Carbamoyl, methylamino carbonyl, ethylamino carbonyl, propyl group amino carbonyl, butyl amino carbonyl, amyl group amino carbonyl, hexyl amino carbonyl, heptyl amino carbonyl, octyl group amino carbonyl, nonyl amino carbonyl, decyl amino carbonyl and phenyl amino carbonyl;

Amino-sulfonyl, dodecyl amino-sulfonyl, N, N-diphenyl amino sulfonyl and N, two (4-chlorphenyl) amino-sulfonyls of N-;

Methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, hexyloxy carbonyl, dodecyloxy carbonyl, octadecane oxygen base carbonyl, phenyloxycarbonyl, (4-tert-butyl group phenoxy group) carbonyl and (4-chlorophenoxy) carbonyl;

Methoxyl group sulfonyl, ethyoxyl sulfonyl, propoxyl group sulfonyl, butoxy sulfonyl, own oxygen base sulfonyl, dodecyloxy sulfonyl, octadecane oxygen base sulfonyl, phenoxy group sulfonyl, 1-and 2-naphthoxy sulfonyl, (4-tert-butyl group phenoxy group) sulfonyl and (4-chlorophenoxy) sulfonyl;

Diphenylphosphino, two (o-tolyl) phosphino-and diphenylphosphine oxygen base;

Fluorine, chlorine, bromine and iodine;

Cyclopropyl; Cyclobutyl, cyclopenta, 2-and 3-methylcyclopentyl; 2-and 3-ethyl cyclopenta; Cyclohexyl, 2-; 3-and 4-methylcyclohexyl, 2-; 3-and 4-ethyl cyclohexyl; 3-and 4-propyl group cyclohexyl; 3-and 4-isopropylcyclohexyl-, 3-and 4-butyl cyclohexyl, 3-and 4-sec-butyl cyclohexyl; 3-and 4-tert-butylcyclohexyl; Suberyl, 2-; 3-and 4-methyl suberyl, 2-; 3-and 4-ethyl suberyl; 3-and 4-propyl group suberyl; 3-and 4-isopropyl suberyl, 3-and 4-butyl suberyl, 3-and 4-sec-butyl suberyl; 3-and 4-tert-butyl group suberyl; The ring octyl group, 2-; 3-; 4-and 5-methyl ring octyl group, 2-; 3-; 4-and 5-ethyl ring octyl group and 3-; 4-and 5-propyl group ring octyl group; 3-and 4-hydroxy-cyclohexyl, 3-and 4-nitrocyclohex base and 3-and 4-chlorine cyclohexyl;

1-, 2-and 3-cyclopentenyl, 1-, 2-, 3-and 4-cyclohexenyl group, 1-, 2-and 3-cycloheptenyl and 1-, 2-, 3-and 4-cyclo-octene base;

2 - 2-

group, a 4 - morpholinyl group, 4 - thiomorpholinyl, 2 - and 3 - tetrahydrofuranyl, 1 -, 2 - and 3 - pyrrolidinyl, 1 - piperazinyl, 1 - dione piperazinyl, and 1 -, 2 -, 3 - and 4 - piperidyl;

Phenyl, 2 - naphthyl, 2 - and 3 - pyrrolyl, 2 -, 3 - and 4 - pyridyl, 2 -, 4 - and 5 - pyrimidinyl, 3 -, 4 - and 5 - pyrazolyl, 2 -, 4 - and 5 - imidazolyl, 2 -, 4 - and 5 - thiazolyl, 3 - (1,2,4 - triazolyl), 2 - (1,3,5 - triazolyl), QUINALDINIC -6 - yl, 3 -, 5 -, 6 - and 8 - quinolyl group, 2 - benzo

yl group, a 2 - benzothiazolyl, 5 - benzo thiadiazolyl, 2 - and 5 - benzimidazolyl, and 1 - and 5 - isoquinolyl;

1-; 2-; 3-; 4-; 5-; 6-and 7-indyl, 1-; 2-; 3-; 4-; 5-; 6-and 7-isoindolyl, 5-(4-methyl isoindolyl); 5-(4-phenyl isoindolyl), 1-; 2-; 4-; 6-; 7-and 8-(1,2; 3; The 4-tetrahydro isoquinolyl), 3-(5-phenyl)-(1,2; 3; The 4-tetrahydro isoquinolyl), 5-(3-dodecyl-(1,2; 3; The 4-tetrahydro isoquinolyl), 1-; 2-; 3-; 4-; 5-; 6-; 7-and 8-(1,2; 3; The 4-tetrahydric quinoline group) and 2-; 3-; 4-; 5-; 6-; 7-and 8-chromanyl, 2-; 4-and 7-quinolyl, 2-(4-phenylchinoline base) and 2-(5-ethyl quinolyl);

2-; 3-and 4-aminomethyl phenyl, 2,4-; 3,5-and 2,6-3,5-dimethylphenyl; 2,4,6-trimethylphenyl, 2-; 3-and 4-ethylphenyl, 2; 4-; 3,5-and 2,6-diethyl phenyl, 2,4; 6-triethyl group phenyl, 2-; 3-and 4-propyl group phenyl, 2,4-; 3,5-and 2; 6-dipropyl phenyl, 2,4,6-tripropyl phenyl, 2-; 3-and 4-isopropyl phenyl; 2,4-; 3,5-and 2,6-diisopropyl phenyl, 2; 4,6-triisopropyl phenyl, 2-; 3-and 4-butyl phenyl, 2,4-; 3; 5-and 2,6-dibutyl phenyl, 2,4; 6-tributyl phenyl, 2-; 3-and 4-isobutyl phenenyl, 2,4-; 3; 5-and 2,6-diisobutyl phenyl, 2,4; 6-triisobutyl phenyl, 2-; 3-and 4-secondary butyl phenenyl, 2,4-; 3; 5-and 2,6-two secondary butyl phenenyls and 2,4,6-three secondary butyl phenenyls; 2-, 3-and 4-methoxyphenyl, 2,4-, 3,5-and 2,6-Dimethoxyphenyl; 2,4,6-trimethoxyphenyl, 2-, 3-and 4-ethoxyl phenenyl; 2,4-, 3,5-and 2,6-diethoxy phenyl; 2,4,6-triethoxy phenyl, 2-, 3-and 4-propoxyl group phenyl; 2,4-, 3,5-and 2,6-dipropoxy phenyl; 2-, 3-and 4-isopropyl phenyl, 2,4-and 2,6-diisopropoxy phenyl and 2-, 3-and 4-butoxy phenyl; 2-, 3-and 4-chlorphenyl and 2,4-, 3,5-and 2,6-dichlorophenyl; 2-, 3-and 4-hydroxy phenyl and 2,4-, 3,5-and 2,6-dihydroxy phenyl; 2-, 3-and 4-cyano-phenyl; 3-and 4-carboxyl phenyl; 3-and 4-carboxamide groups phenyl, 3-and 4-N-methyl carboxamide groups phenyl and 3-and 4-N-ethyl carboxamide groups phenyl; 3-and 4-acetylamino phenyl, 3-and 4-propionamido phenyl and 3-and 4-butyrylamino phenyl; 3-and 4-N-phenylamino phenyl, 3-and 4-N-(o-tolyl) aminophenyl, 3-and 4-N-(tolyl) aminophenyl and 3-and 4-(p-methylphenyl) aminophenyl; 3-and 4-(2-pyridine radicals) aminophenyl, 3-and 4-(3-pyridine radicals) aminophenyl, 3-and 4-(4-pyridine radicals) aminophenyl, 3-and 4-(2-pyrimidine radicals) aminophenyl and 4-(4-pyrimidine radicals) aminophenyl;

4-phenylazo phenyl, 4-(1-naphthyl azo) phenyl, 4-(2-naphthyl azo) phenyl, 4-(4-naphthyl azo) phenyl, 4-(2-pyridylazo) phenyl, 4-(3-pyridylazo) phenyl, 4-(4-pyridylazo) phenyl, 4-(2-pyrimidine radicals azo) phenyl, 4-(4-pyrimidine radicals azo) phenyl and 4-(5-pyrimidine radicals azo) phenyl;

Phenoxy group, thiophenyl, 2-naphthoxy, 2-naphthalene sulfenyl, 2-, 3-and 4-pyridine oxygen base, 2-, 3-and 4-pyridine sulfenyl, 2-, 4-and 5-2-pyrimidinyl oxy and 2-, 4-and 5-pyrimidine sulfenyl.

Preferably fluoridize R ^a, R ^bAnd R ¹-R ¹²Group is as follows:

2; 2; The 2-trifluoroethyl; 2; 2; 3; 3; 3-five fluoropropyls; 2; 2-two fluoro ethyls; 2; 2; 3; 3; 4; 4; 4-seven fluorine butyl; 2; 2; 3; 3; 3-five fluoropropyls; 1H; 1H-15 fluorine octyl groups; 3-bromo-3,3-two fluoropropyls, 3; 3; The 3-trifluoro propyl, 3,3; The 3-trifluoro propyl; 1H, 1H, 2H; 2H-perfluor decyl; 3-(perfluoro capryl) propyl group, 4,4-difluoro butyl; 4; 4,4-trifluoro butyl, 5; 5; 6,6,6-five fluorine hexyls; 2; 2-two fluoropropyls, 2,2; 2-three fluoro-1-phenylethyls are amino; 1-benzyl-2,2, the 2-trifluoroethyl; 2-bromo-2; 2-two fluoro ethyls, 2,2; 2-three fluoro-1-pyridines-2-base ethyl; 2,2-two fluoropropyls, 2; 2; 2-three fluoro-1-(4-methoxyphenyl) ethylamino, 2,2; 2-three fluoro-1-phenethyls; 2,2-two fluoro-1-phenethyls, 1-(4-bromophenyl)-2; 2; The 2-trifluoroethyl, 3-bromo-3,3-two fluoropropyls; 3; 3, the 3-trifluoro propyl is amino, and 3; 3; 3-trifluoro n-pro-pyl, 1H, 1H; 2H; 2H-perfluor decyl, 3-(perfluoro capryl) propyl group, pentafluorophenyl group; 2; 3,5,6-tetrafluoro phenyl; 4-cyanic acid-2; 3,5,6-tetrafluoro phenyl; 4-carboxyl-2; 3,5,6-tetrafluoro phenyl; 2; The 4-difluorophenyl, 2,4; The 5-trifluorophenyl; 2,4, the 6-trifluorophenyl; 2; The 5-difluorophenyl, 2-fluoro-5-nitrobenzophenone, 2-fluoro-5-trifluoromethyl; 2-fluoro-5-aminomethyl phenyl; 2,6-difluorophenyl, 4-carboxamide groups-2; 3; 5,6-tetrafluoro phenyl, 2-bromo-4; The 6-difluorophenyl; 4-bromo-2-fluorophenyl, 2, the 3-difluorophenyl; 4-chloro-2-fluorophenyl; 2,3, the 4-trifluorophenyl; 2-fluoro-4-iodophenyl; 4-bromo-2,3,5; 6-tetrafluoro phenyl; 2,3, the 6-trifluorophenyl; 2-bromo-3; 4,6-trifluorophenyl, 2-bromo-4; 5; The 6-trifluorophenyl, 4-bromo-2,6-difluorophenyl; 2; 3,4,5-tetrafluoro phenyl; 2; 4-two fluoro-6-nitrobenzophenones, 2-fluoro-4-nitrobenzophenone, 2-chloro-6-fluorophenyl; 2-fluoro-4-aminomethyl phenyl; 3-chloro-2,4-difluorophenyl, 2; 4-two bromo-6-fluorophenyls; 3,5-two chloro-2,4-difluorophenyl; 4-cyanic acid-1-fluorophenyl; 1-chloro-4-fluorophenyl, 2-fluoro-3-trifluoromethyl, 2-trifluoromethyl-6-fluorophenyl; 2; 3,4,6-tetrafluoro phenyl; 3-chloro-2-fluorophenyl; 5-chloro-2-fluorophenyl, 2-bromo-4-chloro-6-fluorophenyl, 2; 3-dicyano-4; 5,6-trifluorophenyl, 2; 4; 5-three fluoro-3-carboxyl phenyls, 2,3; 4-three fluoro-6-carboxyl phenyls; 2,3, the 5-trifluorophenyl; 4-trifluoromethyl-2; 3,5,6-tetrafluoro phenyl; 1-fluoro-5-carboxyl phenyl; 2-chloro-4,6-difluorophenyl, 6-bromo-3-chloro-2; The 4-difluorophenyl; 2,3,4-three fluoro-6-nitrobenzophenones; 2; 5-two fluoro-4-cyano-phenyls, 2,5-two fluoro-4-trifluoromethyls; 2; 3-two fluoro-6-nitrobenzophenones, 4-trifluoromethyl-2,3-difluorophenyl; 2-bromo-4; The 6-difluorophenyl, 4-bromo-2-fluorophenyl, 2-nitro tetrafluoro phenyl; 2; 2 ', 3,3 '; 4 '; 5,5 ', 6; 6 '-nine fluorine xenyls; 2-nitro-3,5, the 6-trifluorophenyl; 2-bromo-6-fluorophenyl; 4-chloro-2-fluoro-6-iodophenyl, 2-fluoro-6-carboxyl phenyl, 2; 4-two fluoro-3-trifluorophenyls; 2-fluoro-4-trifluorophenyl, 2-fluoro-4-carboxyl phenyl, 4-bromo-2; The 5-difluorophenyl; 2,5-two bromo-3,4; The 6-trifluorophenyl; 2-fluoro-5-methyl sulphonyl phenyl, 5-bromo-2-fluorophenyl, 2-fluoro-4-hydroxymethyl phenyl; 3-fluoro-4-2-bromomethylphenyl; 2-nitro-4-trifluoromethyl, 4-trifluoromethyl, 2-bromo-4-trifluoromethyl; 2-bromo-6-chloro-4-(trifluoromethyl) phenyl; 2-chloro-4-trifluoromethyl, 3-nitro-4-(trifluoromethyl) phenyl, 2; 6-two chloro-4-(trifluoromethyl) phenyl; The 4-trifluorophenyl, 2,6-two bromo-4-(trifluoromethyl) phenyl; 4-trifluoromethyl-2; 3,5,6-tetrafluoro phenyl; 3-fluoro-4-trifluoromethyl; 2,5-two fluoro-4-trifluoromethyls, 3; 5-two fluoro-4-trifluoromethyls; 2,3-two fluoro-4-trifluoromethyls, 2; Two (trifluoromethyl) phenyl of 4-; 3-chloro-4-trifluoromethyl, 2-bromo-4,5-two (trifluoromethyl) phenyl; 5-chloro-2-nitro-4-(trifluoromethyl) phenyl; 2,4,6-three (trifluoromethyl) phenyl; 3; Two (trifluoromethyl) phenyl of 4-, 2-fluoro-3-trifluoromethyl, 2-iodo-4-trifluoromethyl; 2-nitro-4; Two (trifluoromethyl) phenyl of 5-, 2-methyl-4-(trifluoromethyl) phenyl, 3; 5-two chloro-4-(trifluoromethyl) phenyl; 2,3,6-three chloro-4-(trifluoromethyl) phenyl; 4-(trifluoromethyl) benzyl; 2-fluoro-4-(trifluoromethyl) benzyl, 3-fluoro-4-(trifluoromethyl) benzyl, 3-chloro-4-(trifluoromethyl) benzyl; 4-fluorobenzene ethyl; 3-(trifluoromethyl) phenethyl, 2-chloro-6-fluorobenzene ethyl, 2; 6-dichloro-benzenes ethyl; 3-fluorobenzene ethyl, 2-fluorobenzene ethyl, (2-trifluoromethyl) phenethyl; 4-fluorobenzene ethyl; 3-fluorobenzene ethyl, 4-trifluoromethyl phenethyl, 2; 3-difluoro phenethyl; 3,4-difluoro phenethyl, 2; 4-difluoro phenethyl; 2,5-difluoro phenethyl, 3; 5-difluoro phenethyl; 2,6-difluoro phenethyl, 4-(4-fluorophenyl) phenethyl; 3; 5-two (trifluoromethyl) phenethyl, phenyl-pentafluoride ethyl, 2; 4-two (trifluoromethyl) phenethyl; 2-nitro-4-(trifluoromethyl) phenethyl, (2-fluoro-3-trifluoromethyl) phenethyl, (2-fluoro-5-trifluoromethyl) phenethyl; (3-fluoro-5-trifluoromethyl) phenethyl; (4-fluoro-2-trifluoromethyl) phenethyl, (4-fluoro-3-trifluoromethyl) phenethyl, (2-fluoro-6-trifluoromethyl) phenethyl; (2; 3, the 6-trifluoro) phenethyl, (2; 4; The 5-trifluoro) phenethyl, (2,4; The 6-trifluoro) phenethyl; (2,3, the 4-trifluoro) phenethyl; (3; 4, the 5-trifluoro) phenethyl, (2; 3; The 5-trifluoro) phenethyl, (2-chloro-5-fluorine) phenethyl, (3-fluoro-4-trifluoromethyl) phenethyl; (2-chloro-5-trifluoromethyl) phenethyl; (2-fluoro-3-chloro-5-trifluoromethyl) phenethyl, (2-fluoro-3-chlorine) phenethyl, (4-fluoro-3-chlorine) phenethyl; (2-fluoro-4-chlorine) phenethyl; (2,3-two fluoro-4-methyl) phenethyl, 2; 6-two fluoro-3-chlorobenzene ethyls; (2,6-two fluoro-3-methyl) phenethyl, (2-trifluoromethyl-5-chlorine) phenethyl; (6-chloro-2-fluoro-5-methyl) phenethyl; (2,4-two chloro-5-fluorine) phenethyl, 5-chloro-2-fluorobenzene ethyl; (2; 5-two fluoro-6-chlorine) phenethyl, (2,3; 4; The 5-tetrafluoro) phenethyl, (2-fluoro-4-trifluoromethyl) phenethyl, 2; 3-(two fluoro-4-trifluoromethyls) phenethyl; (2,5-two (trifluoromethyl)) phenethyl, 2-fluoro-3; 5-dibromobenzene ethyl; (3-fluoro-4-nitro) phenethyl, (2-bromo-4-trifluoromethyl) phenethyl, 2-(bromo-5-fluorine) phenethyl; (2; 6-two fluoro-4-bromines) phenethyl, (2,6-two fluoro-4-chlorine) phenethyl; (3-chloro-5-fluorine) phenethyl, (2-bromo-5-trifluoromethyl) phenethyl etc.

In addition, following formula (I) and the hereinafter R described in the formula ^a, R ^bAnd R ¹-R ¹²Instantiation also be:

1H, 1H-perfluor-C ₂-C ₃₀Alkyl or 1H, 1H, 2H, 2H-perfluor-C ₃-C ₃₀Alkyl, preferred 1H, 1H-perfluor-C ₂-C ₂₀Alkyl or 1H, 1H, 2H, 2H-perfluor-C ₃-C ₂₀Alkyl especially is 1H, 1H-perfluor-C ₂-C ₁₀Alkyl or 1H, 1H, 2H, 2H-perfluor-C ₃-C ₁₀Alkyl, as 2,2,2-trifluoroethyl, 2,2,3,3,3-five fluoropropyls, 2; 2,3,3,4,4,4-seven fluorine butyl, 1H, 1H-perfluor amyl group, 1H, 1H-perfluoro hexyl; 1H, 1H-perfluor heptyl, 1H, 1H-15 fluorine octyl groups, 1H, 1H-perfluor nonyl, 1H, 1H-perfluor decyl, 3; 3,3-trifluoro propyl, 3,3,4,4,4-five fluorine butyl, 1H, 1H; 2H, 2H-perfluor amyl group, 1H, 1H, 2H, 2H-perfluoro hexyl, 1H, 1H, 2H; 2H-perfluor heptyl, 1H, 1H, 2H, 2H-perfluoro capryl, 1H, 1H, 2H, 2H-perfluor nonyl.

In the compound of general formula (I), R ^aAnd R ^bGroup preferably is selected from hydrogen, deuterium, unsubstituted alkyl, aralkyl, cycloalkyl, unsubstituted aryl and alkaryl independently of one another.

In the compound of general formula (I), R ^aAnd R ^bGroup more preferably is selected from hydrogen, deuterium, C independently of one another ₁-C ₁₂Alkyl, C ₇-C ₂₂Aralkyl, C ₄-C ₇Cycloalkyl, C ₆-C ₁₀Aryl and C ₇-C ₂₂Alkaryl.

In the compound of general formula (I), R ^aAnd R ^bGroup preferably has identical definition.

In specific embodiments, in the compound of general formula (I), R ^aAnd R ^bThe two is hydrogen group.

In another embodiment, in the compound of general formula (I), R ^aAnd R ^bThe two is deuterium group.

In another embodiment, in the compound of general formula (I), R ^aAnd R ^bThe two is C group ₁-C ₆Alkyl more specifically is methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl or n-hexyl.

In another embodiment, in the compound of general formula (I), R ^aAnd R ^bThe two is phenyl or C group ₁-C ₁₂Alkyl phenyl especially is C ₁-C ₆Alkyl phenyl or the two are naphthyl.

Preferably, in the compound of general formula (I), R ¹-R ¹²Base is selected from hydrogen, F, Cl, hydroxyl, C independently of one another ₁-C ₁₈Alkyl, C ₁-C ₁₂Alkoxyl, C ₁-C ₆Alkylthio group, C ₇-C ₂₂Aralkyl, C ₇-C ₂₂Aralkoxy, C ₇-C ₂₂Aromatic alkylthio, C ₄-C ₇Cycloalkyl, C ₆-C ₁₀Aryl, C ₇-C ₂₂Alkaryl, C ₇-C ₂₂Aryloxy alkyl, C ₇-C ₂₂Alkane arylthio, amino, list (C ₁-C ₁₂Alkyl) amino, two (C ₁-C ₁₂Alkyl) amino, NH (C ₆-C ₁₀Aryl), N (C ₆-C ₁₀Aryl) ₂, heteroaryl and oligomeric heteroaryl, wherein the heteroaryl of heteroaryl and oligomeric heteroaryl can not be substituted independently of one another or is selected from C by 1,2,3 or 4 ₁-C ₁₂Alkyl and C ₁-C ₁₂The group of alkoxyl replaces.

In the compound of general formula (I), R ¹-R ¹²Group preferably is selected from hydrogen, C independently of one another ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkoxyl, phenyl, naphthyl, phenoxy group, naphthoxy and oligomeric thio-phenyl, wherein phenyl, naphthyl, phenoxy group, naphthoxy and oligomeric thio-phenyl are not substituted or have 1 or 2 and be selected from C ₁-C ₁₂Alkyl and C ₁-C ₁₂The substituting group of alkoxyl.

In the compound of general formula (I), 0,1,2,3 or 4 R ¹-R ¹²Base preferably has the definition that is different from hydrogen.In specific embodiments, in the compound of general formula (I), R ¹-R ¹²2 in the group have the definition that is different from hydrogen.

In the compound of general formula (I), at least one R ¹, R ⁵, R ⁸And R ⁹Base has the definition that is different from hydrogen.

The compound of preferred formula (I.1):

Wherein

R ^aAnd R ^bBe selected from hydrogen, deuterium, C independently of one another ₁-C ₆Alkyl, phenyl and naphthyl,

R ¹And R ⁹Be selected from phenyl, phenoxy group, thiophenyl, naphthyl, naphthoxy, naphthalene sulfenyl, (C independently of one another ₁-C ₁₂Alkyl) phenyl, (C ₁-C ₁₂Alkyl) phenoxy group, (C ₁-C ₁₂Alkyl) thiophenyl, (C ₁-C ₁₂Alkyl) naphthyl, (C ₁-C ₁₂Alkyl) naphthoxy and (C ₁-C ₁₂Alkyl) naphthalene sulfenyl,

R ⁵And R ⁸Be selected from hydrogen, hydroxyl and C independently of one another ₁-C ₁₂Alkoxyl.

The instance that preferably is applicable to the indanthrene compound (I) in the organic solar batteries is as follows:

Be used for the indanthrene compound (I) of solar cell of the present invention can be by one of skill in the art known conventional method preparation.

Unsubstituted Yindanshilin (indanthrene blue, indanthrone blue) for example, the name

BlueL6480 purchased from BASF SE.The also commercially available acquisition of many other indanthrene derivatives.

Can through with D ₂SO ₄D is used in reaction then ₂The O deposition prepares on nitrogen-atoms top or the compound of whole deuterates by corresponding protonated compounds.According to required degree of deuterium, this can repeat once or surpass once.

Can be through conventional method by corresponding protonated compounds preparation substituted compound on nitrogen-atoms.

With regard to alkylation, can use the alkylating reagent that is generally used for this purpose, like alkyl halide, alkyl sulfate or alkyl sulfonic ester (like tosylate).

The appropriate method of the corresponding protonated compounds of arylation is through carrying out with the mode catalytic coupling of aryl halide with the C-NUllmann coupling.For example, available aryl bromide (like bromobenzene) arylation indanthrene compound.Appropriate catalyst is a copper catalyst, like CuI and acetate Cu (I).

Before being used for organic solar batteries, can purify to the indanthrene compound.Purification can be by one of skill in the art known conventional method, as separate on mutually in suitable stationary, distillation, extraction, distillation, at least two kinds combination is carried out in crystallization or these methods again.Each is purified and can have a step or a multistep setting.Each purification operations can repeat twice or more times.But different purification operations combination with one another.

In specific embodiments, purifying comprises column chromatography.For this reason, can be on silica gel separate or filter being present in raw material in solvent or the solvent mixture.At last, for example remove said solvent through vapourisation under reduced pressure.Suitable solvents are aromatic compounds such as benzene, toluene, xylene,

, chlorobenzene or dichlorobenzene; hydrocarbons and hydrocarbon mixtures, such as pentane, hexane, ligroin and petroleum ether; halogenated hydrocarbons such as chloroform or dichloro- and said solvent is a mixture of methane.With regard to chromatography, also can use the gradient of at least two kinds of different solvents, like toluene/benzinum gradient.

In another embodiment, purification comprises distillation.This can be preferably fractional sublimation.With regard to fractional sublimation, can be in distillation serviceability temperature gradient and/or deposit unsubstituted indanthrene.In addition, purification can be through being undertaken by the distillation of carrier gas stream.Suitable carrier gas is an inert gas, like nitrogen, argon gas or helium.Load can there be the air-flow of said compound to feed in the separation chamber subsequently.Suitable separation chamber can have a plurality of Disengagement zone that can under different temperatures, move.Preference such as so-called three districts distillation device.The additive method and the unit describe that are used for fractional sublimation be in US4, in 036,594.

Organic solar batteries has layer structure usually and generally includes at least a with lower floor: anode, photosensitive layer and negative electrode.Usually these layers are put on the substrate that is suitable for this purpose.The structure example of organic solar batteries is as being described among US2005/0098726 and the US2005/0224905.

The present invention provides a kind of organic solar batteries that comprises the substrate with at least one negative electrode and at least one anode, its comprise at least a as light-sensitive material like defined general formula (I) compound above.Organic solar batteries of the present invention comprises at least one photosensitive area.The photosensitive area can comprise two layers, and every layer has homogeneous composition and forms plane donor-receiver heterojunction.The photosensitive area also can comprise mixed layer and form the donor-receiver heterojunction that is donor-receiver body heterojunction form.The organic solar batteries that is the photosensitive donor-receiver transition region of having of body heterojunction form is the preferred embodiment of the invention.

The suitable substrate that is used for organic solar batteries for example is oxide material, polymer and combination thereof.Preferred oxide material is selected from glass, pottery, SiO ₂, quartz etc.Preferred polymer is selected from PETG, polyolefin (like polyethylene and polypropylene), polyester, fluoropolymer, polyamide, polyurethane, gathers (methyl) alkyl acrylate, polystyrene, polyvinyl chloride and mixture and composite material.

Suitable electrode (negative electrode, anode) is semiconductor, metal alloy, semiconducting alloy and combination thereof in principle.Preferred metal is those of periodic table the 2nd, 8,9,10,11 or 13 families, like Pt, Au, Ag, Cu, Al, In, Mg or Ca.Preferred semiconductor for example is doping Si, doped with Ge, tin indium oxide (ITO), fluorinated tin (FTO), oxidation gallium indium tin (GITO), zinc indium tin oxide (ZITO) etc.Preferred metal alloy for example is the alloy based on Pt, Au, Ag, Cu etc.Specific embodiments is the Mg/Ag alloy.

Being used for material towards the electrode of light (anode of positive interposed structure, the negative electrode in the inverted structure) is preferably the incident light material of partially transparent at least.This preferably includes has as the glass of carrier material and/or the electrode of transparent polymer.Be suitable for being mentioned those above, like PETG as the transparent polymer of carrier.The electric contact connection is undertaken by metal level and/or transparent conductive oxide (TCO) usually.These preferably include ITO, doped ITO, FTO (fluorine doped tin oxide), AZO (mixing aluminium tin oxide), ZnO, TiO ₂, Ag, Au, Pt.Especially preferably ITO being used for the contact connects.With regard to electric contact connects, also can use conducting polymer, as gather-3,4-alkylene dioxy thiophene, as gather-3,4-enedioxy thiophene (PEDOT).

Towards the electrode of light so that thereby it enough thinly causes only minimum light absorption, yet thereby the enough thick again charge carrier that can make extraction well the mode of charge transfer be provided with.The thickness of said electrode layer (not comprising carrier material) is preferably 20-200nm.

In specific embodiments, the material that is used for the electrode (negative electrode of positive interposed structure, the anode in the inverted structure) back to light is the material of partial reflection incident light at least.This comprises metal film, is preferably the metal film of Ag, Au, Al, Ca, Mg, In and composition thereof.Preferred mixture is Mg/Al.The thickness of said electrode layer is preferably 50-300nm.

The photosensitive area comprise at least one comprise at least a as above defined general formula (I) indanthrene compound the layer or constitute by it.In addition, said photosensitive area can have one deck or a plurality of other layer.These for example are selected from:

-have electric conductivity layer (electron transfer layer, ETL),

-comprise the P-conductivity material layer (hole transmission layer, HTL), it need not to absorb any radiation,

-exciton and hole blocking layer (like EBL), its must not absorb and

-dynode layer.

The suitable material that hereinafter detailed description is used for these layers.Suitable exciton and hole blocking layer for example are described in US6, in 451,415.The suitable material that is used for exciton barrier-layer for example is bathocuproine (BCP), 4,4 ', 4 "-three [3-aminomethyl phenyl-N-phenylamino] triphenylamines (m-MTDATA) or gather enedioxy thiophene (PEDOT).

Solar cell of the present invention comprises at least one photosensitive donor-receiver heterojunction.The optical excitation of organic material produces exciton.In order to produce photoelectric current, the electron-hole pair donor-receiver between two kinds of different slider materials usually separates at the interface.At this at the interface, donor material and acceptor material form heterojunction.When electric charge did not separate, they can be through being also referred to as the process of " quencher ", perhaps has than the more low-energy light of incident light through emission and radiation recombination or through producing heat but not radiation recombination.Said two kinds of processes all are undesirable.According to the present invention, the replacement indanthrene of at least a general formula (I) can be used as electric charge generation body (giving body).When making up with suitable electron acceptor material (ETM, electron transport material), radiation excitation transfers to ETM with electronics subsequently fast.ETM of the present invention is C60 and other fullerenes.

In the first embodiment, has a planar structure of the heterojunction (see: Two Layerorganic Photovoltaic Cell, CWTang, Appl.Phys.Lett., 48 (2) ,183-185 (1986), or N. Karl, A.Bauer, J.

J.Marktanner, M.

F.

Mol.Cryst.Liq.Cryst. ,252,243-258 (1994).).

In second preferred embodiment, said heterojunction is set to body (mixing) heterojunction, is also referred to as the donor-receiver network of IPN.Organic photovoltaic battery with body heterojunction for example is described in C.J.Brabec; N.S.Sariciftci; J.C.Hummelen in Adv.Funct.Mater.; 11 (1); 15 (2001) or J.Xue; B.P.Rand, S.Uchida and S.R.Forrest in J.Appl.Phys.98 is in 124903 (2005).Body heterojunction is set forth hereinafter in detail.

The compound of formula (I) can be used as and have MiM, pin, pn, Mip or Min structure (M=metal, the organic or inorganic semiconductor that p=p mixes, the organic or inorganic semiconductor that n=n mixes, the intrinsic conduction system of i=organic layer; Referring to for example J.Drechsel etc., Org.Electron., 5 (4), 175 (2004) or Maennig etc., Appl.Phys.A 79,1-14 (2004)) battery in light-sensitive material.

Also the compound of formula (I) can be used as the light-sensitive material in the laminated cell.Suitable laminated cell for example is described in P.Peumans, A.Yakimov, S.R.Forrest in J.Appl.Phys, 93 (7); 3693-3723 (2003) (also referring to US4,461,922, US6; 198,091 and US6,198,092) in and will be described in detail hereinafter.It is the preferred embodiments of the invention that the indanthrene compound of general formula (I) is used for laminated cell.

The compound of formula (I) also can be used as by two or surpasses light-sensitive material in the laminated cell that two MiM that pile up, pin, Mip or Min structures constitute (referring to DE 10313232.5 and J.Drechsel etc.; Thin Solid Films; 451452,515-517 (2004)).

The bed thickness of M, n, i and p layer is generally 10-1000nm, more preferably 10-400nm.Form the said layer of solar cell can be by one of skill in the art known conventional method preparation.These methods comprise under reduced pressure or vapour deposition under the inert gas atmosphere, laser ablation or solution or dispersion processing method such as spin coating, scraper coating, casting method, spraying apply, dip-coating or printing be (like ink-jet, flexographic plate, hectograph, gravure; Intaglio plate, nano impression).In specific embodiments, whole solar cell is through the vapour deposition process preparation.

In order to improve the efficient of organic solar batteries, can shorten that exciton arrives next donor-receiver interface and the average distance that must diffuse through.For this reason, can use the donor material of formation interpenetrating networks and the mixed layer of acceptor material, wherein interior donor-receiver heterojunction is possible.This body heterojunction is the particular form of said mixed layer, and wherein the exciton that is produced only need spread very short distance before arriving the border, territory that they are separated.

In preferred embodiments, the photosensitive donor-receiver transition region that is the body heterojunction form is through vapour deposition process (physical vapour deposition (PVD), PVD) preparation.Appropriate method for example is described among the US2005/0227406, quotes the document here.For this reason, the indanthrene compound of general formula (I) and complementary semiconductor materials can carry out vapour depositions with distillation mode altogether.The PVD method is carried out under high vacuum condition and may further comprise the steps: evaporation, transmission, deposition.Deposition is preferably about 10 ^-2-10 ^-7Millibar, for example 10 ^-5-10 ^-7Carry out under the pressure of millibar.Deposition rate is preferably 0.01-10nm/s.Deposition can for example be carried out under nitrogen, helium or argon gas under inert gas atmosphere.Underlayer temperature in the deposition process is preferably-100 ° of C to 300 ° of C, more preferably-50 ° C to 250 ° of C.

Other of said organic solar batteries layer can be through known method preparation.These methods comprise under reduced pressure or vapour deposition in the inert gas atmosphere, laser ablation or solution or dispersion processing method such as spin coating, scraper coating, casting method, spraying apply, dip-coating or printing be (like ink-jet, flexographic plate, hectograph, gravure; Intaglio plate, nano impression).In specific embodiments, whole solar cell is through the vapour deposition process preparation.

Photosensitive layer (conforming layer or mixed layer) is heat-treated after can constituting other layers of solar cell in its preparation back or in preparation immediately.In many cases, this heat treatment can further improve the pattern of photosensitive layer.Temperature is preferably about 60-300 ° C.Processing time is preferably 1 minute to 3 hours.Except perhaps replacing heat treatment, said photosensitive layer (mixed layer) is handled with solvent-laden gas after can constituting other layers of solar cell in its preparation back or in preparation immediately.In suitable embodiment, use solvent vapour saturated in air at ambient temperature.Suitable solvent is toluene, xylenes, chloroform, N-methyl pyrrolidone, dimethyl formamide, ethyl acetate, chlorobenzene, carrene and composition thereof.Processing time is preferably 1 minute to 3 hours.

In preferred embodiments, solar cell of the present invention exists as the single battery with the positive interposed structure of planar heterojunction.Fig. 1 has shown the solar cell of the present invention with positive interposed structure.In specific embodiments, said battery has following structure:

-the conductive layer of partially transparent (top electrode, anode) (11) at least

-hole-conductive layer (hole transmission layer, HTL) (12)

-comprise the layer (13) of donor material

-comprise the layer (14) of acceptor material

-exciton barrier-layer and/or electronic conductive layer (15)

-the second conductive layer (back electrode, negative electrode) (16)

Said donor material preferably includes at least a formula (I) compound or is made up of formula (I) compound.According to the present invention, said acceptor material comprises at least a fullerene or fullerene derivate, perhaps is made up of fullerene or fullerene derivate.Said acceptor material preferably comprises C60 or PCBM ([6,6]-phenyl-C61-methyl butyrate).

As stated, the conductive layer of substantially transparent (11) (anode) comprises carrier, like glass or polymer (like PETG) and electric conducting material.Instance comprises ITO, FTO, ZnO, AZO of ITO, doping etc.Can for example use UV light, ozone, oxygen plasma, Br ₂Carry out surface treatment Deng the antianode material.Layer (11) thus not only should enough approach and can absorb maximum light, thereby and should enough thickly guarantee good charge transfer.The bed thickness of said transparency conducting layer (11) is preferably 20-200nm.

The solar cell with positive interposed structure of Fig. 1 is chosen wantonly has hole-conductive layer (HTL).This layer comprise at least a hole-conductive material (hole mobile material, HTM).Layer (12) can be the basic individual course of composition uniformly maybe can comprise two or surpass two sub-layer.

The hole-conductive material (HTM) that is suitable for forming the layer (HTL) with hole-conductive performance preferably comprises at least a material with high ionization ability.Ionization energy is preferably 5.0eV at least, more preferably 5.5eV at least.Said material can be the organic or inorganic material.Be applicable to that the organic material in the layer with hole-conductive performance is preferably selected from and gathers (3; 4-enedioxy thiophene) gather (styrene sulfonate) (PEDOT-PSS), Ir-DPBIC (three-N, N '-diphenyl benzo imidazoles-2-subunit iridium (III)), N, N '-diphenyl-N; N '-two (3-aminomethyl phenyl)-1; 1 '-diphenyl-4,4 '-diamines (α-NPD), 2,2 '; 7; 7 '-four (N, N-di-p-methoxy phenyl amine)-9,9 '-spiral shell, two fluorenes (spiral shell-MeOTAD) wait and composition thereof.Need, said organic material can be doped with p type dopant, and said dopant has that HOMO with the hole-conductive material is in same range as or than its lower LUMO.Suitable dopant for example is 2,3,5,6-tetrafluoro-7,7,8,8-four cyano benzoquinones bismethane (F ₄TCNQ), WO ₃, MoO ₃Deng.Be applicable to that the inorganic material in the layer with hole-conductive performance is preferably selected from WO ₃, MoO ₃Deng.

If present, the thickness with layer of hole-conductive performance is preferably 5-200nm, more preferably 10-100nm.

Layer (13) comprises the compound of at least a general formula (I).The thickness of said layer should not only be enough to absorb the light of maximum, thereby and should enough approach electric charge is effectively dissipated.The thickness of layer (13) is preferably 5nm to 1 μ m, more preferably 5-80nm.

Layer (14) comprises at least a acceptor material.According to the present invention, said acceptor material comprises at least a fullerene or fullerene derivate.The thickness of said layer should not only be enough to absorb the light of maximum, thereby and should enough approach electric charge is effectively dissipated.The thickness of layer (14) is preferably 5nm to 1 μ m, more preferably 5-80nm.

The solar cell with positive interposed structure of Fig. 1 is optional to comprise exciton barrier-layer and/or electronic conductive layer (15) (EBL/ETL).The material that is applicable to exciton barrier-layer has the bigger band gap of material than layer (13) and/or (14) usually.It at first can reflect exciton, secondly can pass through said layer transmission electronic well.The material that is used for layer (15) can comprise organic or inorganic material.Suitable organic material is preferably selected from 2,9 - dimethyl -4,7 - diphenyl-1, 10 - phenanthroline (BCP), 4,7 - diphenyl-1, 10 - phenanthroline ( Bphen), 1,3 - bis [2 - (2,2 - United pyridin-6 - yl) -1,3,4 -

oxadiazol-5 - yl] benzene (BPY-OXD) and so on.Need, said organic material can be doped with n type dopant, and said dopant has that LUMO with electrically conductive material is in same range as or than its lower HOMO.Suitable dopant for example is Cs ₂CO ₃, Pyronine B (PyB), rhodamine B, cobaltocene etc.Be applicable to that the inorganic material in the layer with electrical conductivity performance is preferably selected from ZnO etc.If present, the thickness of layer (15) is preferably 5-500nm, more preferably 10-100nm.

Layer 16 is negative electrode and preferably comprise at least a compound with low work content, and more preferably metal is like Ag, Al, Mg, Ca etc.The thickness of layer (16) is preferably about 10nm to 10 μ m, like 10-60nm.

In preferred embodiments, solar cell of the present invention exists as the single battery with planar heterojunction and inverted structure.Fig. 2 has shown the solar cell with inverted structure.In specific embodiments, said battery has following structure:

-the conductive layer of partially transparent (negative electrode) (11) at least

-exciton barrier-layer and/or electronic conductive layer (12)

-comprise the layer (13) of acceptor material

-comprise the layer (14) of donor material

-hole-conductive layer (hole transmission layer, HTL) (15)

-the second conductive layer (back electrode, anode) (16)

With regard to the suitable and preferable material that is used for layer (11)-(16), with reference to above about the description of the equivalent layer in the solar cell with positive interposed structure.

In another preferred embodiment, solar cell of the present invention exists as the single battery with positive interposed structure and body heterojunction.Fig. 3 has shown the solar cell with body heterojunction.In specific embodiments, said battery has following structure:

-the conductive layer of partially transparent (anode) (21) at least

-hole-conductive layer (hole transmission layer, HTL) (22)

-comprising the mixed layer of donor material and acceptor material, its formation is the donor-receiver heterojunction (23) of body heterojunction form

-electronic conductive layer (24)

-exciton barrier-layer and/or electronic conductive layer (25)

-the second conductive layer (back electrode, negative electrode) (26)

Layer (23) comprises at least a as light-sensitive material, especially as general formula (I) the indanthrene compound of donor material.Layer (23) additionally preferably comprises at least a fullerene or fullerene derivate as acceptor material.Layer (23) especially comprises C60 or PCBM ([6,6]-phenyl-C61-methyl butyrate) as acceptor material.

With regard to layer (21), all with reference to above about the description of layer (11).

With regard to layer (22), all with reference to above about the description of layer (12).

Layer (23) is for comprising the compound of at least a general formula as donor material (I), i.e. fullerene or fullerene derivate.In addition, layer (23) comprises at least a acceptor material.As stated, layer (23) can use conventional solvent preparation through coevaporation or solution processing.Said mixed layer comprises based on this mixed layer total weight and is preferably 10-90 weight %, more preferably the compound of at least a general formula (I) of 20-80 weight %.Said mixed layer comprises based on this mixed layer total weight and is preferably 10-90 weight %, more preferably at least a acceptor material of 20-80 weight %.The thickness of layer (23) should not only be enough to absorb the light of maximum, thereby and should enough approach electric charge is effectively dissipated.The thickness of layer (23) is preferably 5nm to 1 μ m, and more preferably 5-200nm especially is 5-80nm.

The solar cell with body heterojunction of Fig. 3 comprises electronic conductive layer (24) (ETL).This layer comprises at least a electron transport material (ETM).Layer (24) can be the individual layer of basic composition uniformly or can comprise two or surpass two sub-layer.The suitable material that is used for electronic conductive layer has low work content or ionization energy usually.Ionization energy preferably is not more than 3.5eV.Suitable organic material is preferably selected from the group described above fullerene and fullerene derivative, 2,9 - dimethyl -4,7 - diphenyl-1, 10 - phenanthroline (BCP), 4 7 - diphenyl-1, 10 - phenanthroline (Bphen), 1,3 - bis [2 - (2,2 '- United pyridin-6 - yl) -1,3,4 -

oxadiazol-5 - yl] benzene (BPY-OXD) and so on.Need, the organic material that is used for layer (24) can be doped with n type dopant, and said dopant has that LUMO with electrically conductive material is in same range as or than its lower HOMO.Suitable dopant for example is Cs ₂CO ₃, Pyronine B (PyB), rhodamine B, cobaltocene etc.If present, the thickness of layer (23) is preferably 1nm to 1 μ m, especially is 5-60nm.

With regard to layer (25), all with reference to above about the description of layer (15).

With regard to layer (26), all with reference to above about the description of layer (16).

Solar cell with the donor-receiver heterojunction that is the body heterojunction form can be through aforesaid vapour deposition process preparation.With regard to underlayer temperature in deposition rate, the deposition process and hot reprocessing, with reference to above describing.

In another preferred embodiment, solar cell of the present invention exists as the single battery with inverted structure and body heterojunction.Fig. 4 has shown the solar cell with body heterojunction and inverted structure.

In another particularly preferred embodiment, solar cell of the present invention is a laminated cell.

Laminated cell is by two or surpass two (as 3,4,5 etc.) sub-batteries and constitute.Single sub-battery, an a little battery or all sub-batteries can have photosensitive donor-receiver heterojunction.Each donor-receiver heterojunction can be planar heterojunction form or body heterojunction form.Preferably, at least a donor-receiver heterojunction is the body heterojunction form.According to the present invention, the photosensitive layer of at least one sub-battery comprises the indanthrene compound of general formula (I).Preferably, the photosensitive layer of at least one sub-battery comprises indanthrene compound and at least a fullerene or the fullerene derivate of general formula (I).More preferably, the semiconductor mixtures of photosensitive layer that is used at least one sub-battery is by the indanthrene compound and the C of general formula (I) ₆₀Or [6,6]-phenyl-C61-methyl butyrate constitutes.

Forming the sub-battery of laminated cell can parallel connection or be connected in series.The sub-battery that forms said laminated cell preferably is connected in series.In each case, preferably between each sub-battery, has extra composite bed.Said each sub-battery has identical polarity, promptly will only have the battery of positive interposed structure usually or only have the battery combination with one another of inverted structure.

Fig. 5 has shown the basic structure of laminated cell of the present invention.Layer 31 is a transparency conducting layer.Suitable material for above to each battery described those.

Layer 32 and 34 constitutes sub-battery.Here, " sub-battery " is meant the above defined battery that does not have negative electrode and anode.Said sub-battery can for example all have be used for photosensitive layer general formula of the present invention (I) indanthrene compound (preferably with fullerene or fullerene derivate; Especially with C60 combination) or have other combinations of semi-conducting material, the for example combination of C60 and Phthalocyanine Zinc, C60 and Oligopoly thiophene (like DCV5T).In addition, each sub-battery also can be arranged to DSSC or polymer battery.In all cases, be preferably the combination of materials of the zones of different of utilizing incident light (like natural sunlight) spectrum.For example, absorb in the Long wavelength region that is combined in sunlight of used general formula (I) the indanthrene compound of the present invention and fullerene or fullerene derivate.Dibenzo two indenos (1,2,3-CD:1 ', 2 ', 3 '-LM) perylene (DBP)-C60 mainly absorbs in the 400-600nm zone.Phthalocyanine Zinc-C60 battery mainly absorbs in the 600-800nm zone.Therefore, the laminated cell that constitutes by this a little battery combination should be in the 400-800nm zone absorbed radiation.Therefore, the appropriate combination of sub-battery should make the spectral range of being utilized be able to enlarge.In order to obtain optimum performance, should consider optical interference.For example, compare with the sub-battery with more long wave absorption, the sub-battery that absorbs at the shorter wavelength place should be more near the metal roof contact.

With regard to layer (31), all with reference to above about the description of layer (11) and (21).

With regard to layer (32) and (34), all with reference to above about layer (12)-(15) that are used for planar heterojunction and be used for body heterojunction layer the description of (22)-(25).

Layer 33 is a composite bed.Composite bed can make from those of the charge carrier of a sub-battery and adjacent sub-battery compound.Suitable is little metal cluster, for example the combination of Ag, Au or height n type and p type doped layer.Under the situation of metal cluster, layer thickness is preferably 0.5-5nm.Under the situation of height n type and p type doped layer, layer thickness is preferably 5-40nm.Said composite bed is connected the electronic conductive layer of sub-battery usually with the hole-conductive layer of adjacent sub-battery.In this way can be with other battery combination to form laminated cell.

Layer 36 is a top electrode.Said material depends on the polarity of sub-battery.With regard to the sub-battery with positive interposed structure, the preferred metal with low work content that uses is like Ag, Al, Mg, Ca etc.With regard to the sub-battery with inverted structure, the preferred metal with high work content that uses is like Au or Pt or PEDOT-PSS.

Under the situation that sub-battery is connected in series, total voltage equals each voltage sum of all sub-batteries.On the contrary, total current receives the restriction of the minimum current of a sub-battery.Based on this reason, thereby the thickness of each sub-battery should be optimized and makes all sub-batteries all have essentially identical electric current.

The instance of different types of donor-receiver heterojunction is the donor-receiver bilayer with planar heterojunction, and perhaps said heterojunction is set to the body heterojunction form of hybrid planar-mixed heterojunction or gradient body heterojunction or annealing.

The preparation of hybrid planar-mixed heterojunction is described in Adv.Mater.17, among the 66-70 (2005).In this structure, be present in evenly and give between body and the acceptor material through evaporating mixed heterojunction layer that acceptor and donor material form simultaneously.

In specific embodiments of the present invention, said donor-receiver heterojunction is the body heterojunction form in gradient.In by the mixed layer of constituting for body and acceptor material, the ratio of donor-receiver gradually changes.Gradient profile can be staged (Fig. 6 (a)) or linearity.In Fig. 6 (a), layer 01 is made up of 100% donor material, the ratio of giving body/acceptor of layer 02>1, ratio=1 of giving body/acceptor of layer 03, the ratio of giving body/acceptor of layer 04 1, and layer 05 is made up of 100% acceptor material.In Fig. 6 (b), layer 01 is made up of 100% donor material, and layer 02 has the ratio of giving body/acceptor of reduction, and promptly the ratio of donor material descends with linear mode on the direction of layer 03, and layer 03 is made up of 100% acceptor material.The ratio of different donor-receivers can be regulated through the deposition rate of every kind of material.This structure can improve the leak path of electric charge.

In another specific embodiments of the present invention, the body heterojunction form that said donor-receiver heterojunction is set to anneal; For example referring to Nature 425,158-162,2003.The method for preparing this solar cell comprises the annealing steps before or after the metal deposition.Because annealing gives body and acceptor material separable, this causes leak path to enlarge more.

In another specific embodiments of the present invention, said organic solar batteries is through the organic vapor phase deposition method, with plane or the preparation of controlled heterojunction structural form.This solar cell is described in Materials, in 4,2005,37.

In specific embodiments, with the replacement indanthrene of at least a general formula (I) as unique electron donor material.

Organic solar batteries of the present invention comprises that at least one comprises the photosensitive area that the indanthrene compound of body is given at least a conduct, and it contacts with at least a fullerene compound as acceptor.Fullerene and fullerene derivate are preferably selected from C ₆₀, C ₇₀, C ₈₄, phenyl-C ₆₁-methyl butyrate ([60] PCBM), phenyl-C ₇₁-methyl butyrate ([71] PCBM), phenyl-C ₈₄-methyl butyrate ([84] PCBM), phenyl-C ₆₁-butyl butyrate ([60] PCBB), phenyl-C ₆₁-n-octyl butyrate ([60] PCBO), thienyl-C ₆₁-methyl butyrate ([60] ThCBM) and composition thereof.Especially preferred C ₆₀, [60] PCBM and composition thereof.

Except that indanthrene compound and fullerene, hereinafter listed semi-conducting material is applicable in the solar cell of the present invention in principle.Said material is given body or acceptor as the sub-battery of laminated cell, itself and the used sub-battery combination of indanthrene/fullerene of the present invention.

Other suitable semiconductors are phthalocyanine.The phthalocyanine that these comprise non-halo or have 1-16 halogen atom.Phthalocyanine is containing metal or contain divalent metal or the group of containing metal atom not.Be preferably based on the phthalocyanine of zinc, copper, iron, titanyl, vanadium oxygen base etc.Especially preferred CuPc, Phthalocyanine Zinc, metal-free phthalocyanine.In specific embodiments, use halogenated phthalocyanines.These comprise: 2,6,10, and 14-tetrafluoro phthalocyanine, as 2,6,10,14-tetrafluoro CuPc and 2,6,10,14-tetrafluoro Phthalocyanine Zinc; 1,5,9,13-tetrafluoro phthalocyanine, as 1,5,9,13-tetrafluoro CuPc and 1,5,9,13-tetrafluoro Phthalocyanine Zinc; 2,3,6,7,10,11,14,15-octafluoro phthalocyanine, as 2,3,6,7,10,11,14,15-octafluoro CuPc and 2,3,6,7,10,11,14,15-octafluoro Phthalocyanine Zinc; The phthalocyanine that is suitable as acceptor for example is ten chlordene phthalocyanines and ten hexafluoro phthalocyanines, like ten chlordene CuPcs, ten chlordene Phthalocyanine Zinc, no metal ten chlordene phthalocyanines, ten hexafluoro CuPcs, ten hexafluoro phthalocyanines or there are not metal ten hexafluoro phthalocyanines.

Other the suitable semiconductors that mainly are suitable as acceptor are naphthalene embedding benzene class (rylenes).With regard to the present invention, naphthalene embedding benzene class is generally understood as the compound of the molecular structure of the naphthalene unit that means Ju You perylene-connection.According to the quantity of naphthalene unit, said compound is Ke Wei perylene (n=2), three naphthalene embedding benzene (n=3), four naphthalene embedding benzene (n=4) or senior naphthalene embedding benzene for example.Therefore, it can be following formula De perylene, three naphthalene embedding benzene or four naphthalene embedding benzene:

Wherein

As far as n=1-4, R ^N1, R ^N2, R ^N3And R ^N4Group is hydrogen, halogen or the group that is different from halogen independently of one another,

Y ¹Be O or NR ^a, R wherein ^aBe hydrogen or organic group,

Y ²Be O or NR ^b, R wherein ^bBe hydrogen or organic group,

Z ¹, Z ², Z ³And Z ⁴The O that respectively does for oneself,

Wherein, at Y ¹Be NR ^aSituation under, Z ¹And Z ²One of group also can be NR ^c, R wherein ^aAnd R ^cGroup is the bridge joint group with 2-5 atom between the side joint key together, and

Wherein, at Y ²Be NR ^bSituation under, Z ³And Z ⁴One of group also can be NR ^d, R wherein ^bAnd R ^dGroup is the bridge joint group with 2-5 atom between the side joint key together.

Suitable naphthalene embedding benzene class for example is described among WO2007/074137, WO2007/093643 and the WO2007/116001, here with reference to these documents.

The also suitable body-semi-conducting material of giving that has hereinafter, it can for example be used for laminated cell, and other sub-batteries that are used for as mentioned below are to replace indanthrene compound (I).

Be suitable for as the semiconductor of giving body be the porphyrin class as 5,10,15,20-four (3-pyridine radicals) porphyrin (TpyP), or four benzoporphyrin classes are like no metal four benzoporphyrins, four benzoporphyrin copper or four benzoporphyrin zinc.Especially be preferably four benzoporphyrin classes.These can be converted into photosensitive component by the solution processing of solubility precursor and through thermal decomposition on substrate.

Being suitable for as other semiconductors of giving body is the acene class.In each case, these are preferably selected from and do not replace or substituted anthracene, aphthacene or pentacene.Substituted acene class preferably comprises at least one and is selected from the substituting group to electron substituent group, electron-withdrawing substituent and combination thereof.Suitable for example is alkyl, alkoxyl, ester group, carboxylic acid ester groups or thio alkoxy to electron substituent group.Suitable electron-withdrawing substituent for example is halogen, nitro or cyanic acid.Preferred acene class is selected from 2,9-dialkyl group pentacene, 2,10-dialkyl group pentacene, 2,10-dialkoxy pentacene, 1,4,8,11-four alkoxyl pentacenes and rubrene (5,6,11,12-tetraphenyl aphthacene).Suitable substituted pentacenes class description is in US2003/0100779 and US6, in 864,396, here with reference to these documents.Especially preferred acene class is a rubrene.

Being suitable for as other semiconductors of giving body is liquid crystal material (LC material).These are preferably selected from coronene class and benzophenanthrene class.Preferred liquid crystal material is six benzo coronene (HBC-PhC ₁₂), coronene imidodicarbonic diamide class, 2,3,6,7,10,11-six hexyl sulfo-benzophenanthrene (HTT ₆), 2,3,6,7,10,11-six (4-n-nonyl phenyl) benzophenanthrene (PTP ₉) or 2,3,6,7,10,11-six (hendecane oxygen base) benzophenanthrene (HAT ₁₁).Especially be preferably the discotic mesogenic material.

Being suitable for as other semiconductors of giving body is thiophenes.These are preferably selected from thiophene, Oligopoly thiophene and substitutive derivative thereof.Suitable Oligopoly thiophene is four thiophene; Five thiophene; Six thiophene; α, ω-two (C ₁-C ₈) alkyl Oligopoly thiophene such as α, ω-dihexyl four thiophene, α, ω-dihexyl five thiophene and α, ω-dihexyl six thiophene; Gather alkylthrophene as gathering (3-hexyl thiophene); Two (two thienothiophenes); Two thiophene-based of anthra and the two thiophene-based of dialkyl group anthra such as the two thiophene of dihexyl anthra; Phenylene thiophene (P-T) oligomer and derivative thereof especially are α, the substituted phenylene thiophene oligomers of ω-alkyl.

Be suitable for being preferably selected from following compound: like α as semi-conductive other thiophenes; α '-two (2; The 2-dicyanovinyl) five thiophene (DCV5T), (3-(4-octyl phenyl)-2; 2 '-two thiophene) (PTOPT), gather-3-(4 '-(1; 4,7-trioxa octyl group) phenyl) thiophene (PEOPT), (gathering (3-(2 '-methoxyl group-5 '-octyl phenyl) thiophene)) (POMeOPT), gather (3-octyl group thiophene) (P ₃OT), gather [2,6-(4, two (2-the ethylhexyl)-4H-cyclopentas of 4-[2,1b; 3,4b '] two thiophene)-4,7-(2,1, the 3-diazosulfide) (PCPDTBT) and gather (pyrido-pyrazine ethenylidene)-polythiophene blend, like EHH-PpyPz, PTPTB copolymer, BBL, F ₈BT, PFMO (referring to Brabec C., Adv.Mater., 2996,18,2884).

Be suitable for being to the penylene ethenylidene and comprising oligomer or copolymer to penylene ethenylidene unit as other semiconductors of giving body.These are preferably selected from polyparaphenylene's ethenylidene, MEH-PPV (gathers (2-methoxyl group-5-(2 '-ethyl hexyl oxy)-1; 4-penylene ethenylidene), MDMO-PPV (gathers (2-methoxyl group-5-(3 '; 7 '-dimethyl octyloxy)-1,4-penylene ethenylidene)), PPV, CN-PPV (derivative) and penylene ethylidene/penylene ethenylidene hybridized polymer (PPE-PPV) with various alkoxyls.

Be suitable for as other semiconductors of giving body for gathering fluorenes and alternately gathering fluorene copolymer.These are preferably selected from 4, and 7-two thiophene-2 '-Ji-2,1, gather (9,9 '-dioctyl fluorene-copolymerization-diazosulfide) (F at the 3-diazosulfide ₈BT) and gather (9,9 '-dioctyl fluorene-copolymerization-two-N, N '-(4-butyl phenyl)-two-N, N '-phenyl-1,4-phenylenediamine (PFB).

Being suitable for as other semiconductors of giving body is polycarbazole, promptly comprises the oligomer and the polymer of carbazole.

Being suitable for as other semiconductors of giving body is polyaniline, promptly comprises the oligomer and the polymer of aniline.

Be suitable for being triarylamine, gathering triarylamine, dicyclopentadiene, polypyrrole, gathering furans, gathering sila cyclopentadiene (polysilole), gathering phosphene, TPD, CBP, spiral shell-MeOTAD as other semiconductors of giving body.

In preferred embodiments, solar cell of the present invention has with lower floor:

ITO

The indanthrene compound of formula (I)

C60

BPhen (=4,7-diphenyl-1,10-phenanthroline)

Ag

Solar cell of the present invention is laminated cell more preferably, and one of them sub-battery has the photosensitive area that comprises at least a formula (I) indanthrene compound and C60.

All above-mentioned semiconductor equalizings can be doping.Semi-conductive conductivity can use dopant to improve through the chemical doping technology.Organic semiconducting materials can be close to or higher than the n type dopant doping of electrically conductive material lumo energy with the HOMO energy level.The p type dopant that the also available lumo energy of organic semiconducting materials is close to or higher than electrically conductive material HOMO energy level mixes.In other words, under the situation that the n type mixes, electronics is discharged by the dopant that is used as to body, and under the situation that the p type mixes, said dopant is as the acceptor of accepting electronics.

The suitable dopants that is used for used indanthrene compound of the present invention and p N-type semiconductor N for example is selected from WO usually ₃, MoO ₃, 2,3,5,6-tetrafluoro-7,7,8,8-four cyano benzoquinones bismethane (F ₄-TCNQ), 3,6-two fluoro-2,5,7,7,8,8-six cyano quinolines bismethanes, DDQ (DDQ) or four cyano benzoquinones bismethane (TCNQ).Preferred dopant is 3,6-two fluoro-2,5,7,7,8,8-six cyano quinolines bismethanes.

The suitable dopants that is used for the used p N-type semiconductor N of the present invention for example is selected from Cs usually ₂CO ₃, LiF, Pyronine B (PyB), rhodamine derivative, cobaltocene etc.Preferred dopant is Pyronine B and rhodamine derivative, especially is rhodamine B.

Said dopant is usually to be 10mol%, the preferably amount of 5mol% use at the most at the most based on the amount of treating doped semiconductor.

Reference hereinafter unrestricted embodiment is set forth the present invention in detail.

Embodiment

I) preparation embodiment

Embodiment 1: the indanthrene blue of deuterate

With the 3.0g indanthrene blue at room temperature at 30mol D ₂SO ₄The middle stirring 20 hours.Then said solution is added into 100ml D ₂To precipitate said product, filter and use D among the O ₂O cleans to neutral.This obtains the 2.98g product.This product is dissolved in 30ml D once more ₂SO ₄In and at room temperature stirred 20 hours.Thereafter Dropwise 5 0ml D ₂O, filtering gained sediment and with residue D ₂O cleans and is dry.This obtains 2.9g deuterate product.

In order to prepare solar cell, this material of 2.0g is carried out gradient distillation three times under 375 ° C/325 ° C/250 ° of C.This obtains the 829mg blue product.

Embodiment 2:N, N '-diphenyl indanthrene

The mixture of 20.0g (45.2mmol) indanthrene blue, 28.5g (182mmol) bromobenzene, 19.25g (182mmol) sodium carbonate, 0.2g (3.18mmol) cupric iodide (I) and 0.34g (1.8mmol) copper acetate (I) was heated 18 hours in 50ml nitrobenzene.With said reactant mixture cooling and via the filter suction strainer that is filled with silica gel.Use the said product of mixture wash-out of acetone and carrene.Use cyclohexane/ethyl acetate (2:1) the thus obtained product of purifying through chromatography once more.This obtains 1.8g (7%) blue solid.

This product of 630mg is carried out the gradient distillation under 265 ° C/200 ° C/150 ° of C.This obtains the 160mg blue material, uses it for the preparation solar cell.

Embodiment 3:N, N '-dimethyl indanthrene

Add 40.0g (90.4mmol) indanthrene blue in the mixture of (856mmol) methyl tosylate of the 160g in being in the 1.4L trichloro-benzenes and 120g (872mmol) potash, and said mixture is heated to reflux reaches 120 hours.Said reactant mixture is cooled to 120 ° of C and under this temperature, filters.The filtering solvent also uses silica gel with crude product, with toluene/carrene (10:1), uses absolute dichloromethane to carry out chromatogram then and purifies.This obtains the 4.96g product, and it is carried out the gradient distillation.

Embodiment 4:4,4 '-dimethoxy indanthrone

4.11-methoxyl group-4-nitroanthraquinone

To be in 10.77g (40mmol) 1-hydroxyl-4-nitroanthraquinone, 3.8g (27.5mmol) potash, 9.28g (50mmol) methyl tosylate in the 60ml dichloro-benzenes is heated to 178 ° of C and reaches 4 hours.Cool off said reactant mixture then and be poured on the 200ml frozen water, filter the residue of this two-phase mixture, through stirring with softened water extraction and drying under reduced pressure.This obtains the cream-coloured product of 10.5g (93%), under further not purifying, it is being used for next step.

4.21-methoxyl group-4-amino anthraquinones

The mixture that will be in 7.5g (26mmol) 1-methoxyl group-4-nitroanthraquinone in the 240ml water, 19.96g (154mmol) vulcanized sodium heated 30 minutes down refluxing.With the cooling of said reactant mixture and be added in the 500ml saturated nacl aqueous solution.Suction strainer filtering residue also cleans with watery hydrochloric acid.This obtains 6.5g (90%) red solid, under further not purifying, uses it for next step.

4.34,4 '-dimethoxy indanthrone

With 4.0g (16mmol) 1-methoxyl group-4-amino anthraquinones, 12.17g (107mmol) N, the mixture of N '-dimethyl propylene thiazolinyl urea and 3.5g 50%KOH solution is heated to 130 ° of C, introduces air simultaneously.Heat said mixture until in thin-film chromatography, no longer detecting reactant.With the cooling of said reactant mixture and be poured into waterborne, the filtering residue.Said product is passed through by N-methyl pyrrolidone crystallization and purification.Identify target compound based on its solid state spectrum (referring to Fig. 8) and through MALDI-MS.

MALDI-MS：503.051[M+H] ⁺，489.045，475.030。

Embodiment 5:5,5 '-two phenoxy group indanthrone

5.11-phenoxy group-5-nitroanthraquinone

To be in the 10.0g (33.5mmol) 1 in the 200ml N-methyl pyrrolidone, the mixture of 5-dinitroanthraquinone, 3.16g (33.5mmol) phenol and 27.8g (201mmol) potash stirred 2 hours under 40 ° of C.Be poured into said reactant mixture on 5% sulfuric acid and stirred 1 hour, suction strainer leaches the cream-coloured sediment of deposition, and water cleans and be dry.This obtains 10.3g (89%) crude product, and it is purified through recrystallization., said crude product is dissolved in the ethyl acetate, the said residue of filtering also passes through to add benzinum by the said product of said solution precipitation for this reason.This obtains 1.67g (15%).

5.21-phenoxy group-5-amino anthraquinones

As described in embodiment 4.2, reduce.Obtain target compound with 91% productive rate.

5.3 5,5 '-two phenoxy group indanthrone

Like synthesising target compound as described in the embodiment 4.3.By Soxhlet extractron by ethanol and the chlorobenzene said target compound of purifying, and by the sulfuric acid fractional crystallization.Differentiate said target compound based on its solid state spectrum (referring to Fig. 9) and through MALDI-MS.

MALDI-MS:826.236,649.137[M+Na] ^-, 627.156[M+H] ⁺, 611.158,550.143,455.329 and 441.309.

II) performance

Through gradient distillation purification indanthrene blue:

Through the said material of gradient distillation purification 2.0g.For this reason, at first remove impurity through distillation under 250 ° C/225 ° C/200 ° of C.Except that the impurity of desublimation and with the distillation once more under 350 ° C/325 ° C/300 ° of C of gained material.This obtains the 1.1g product, with its distillation once more under uniform temp gradient (350 ° C/325 ° C/300 ° of C).This obtains the 916mg product, uses uniform temp gradient (350 ° C/325 ° C/300 ° of C) with said product distillation of 500mg and acquisition 420mg product.This material is used to prepare solar cell.

Fig. 7 has shown the absorption spectrum of the vapor-deposited film of indanthrene blue.Observe long wave and absorb, and have good voltage V _Oc

Substrate:

ITO is sputtered onto on the glass substrate with the thickness of 100nm.Than resistivity is 200 μ Ω cm, mean roughness (RMS; Root mean square) less than 5nm.The deposition other the layer before, with said substrate under UV light with ozone treatment 20 minutes (UV-ozone clean).

The preparation battery:

At high vacuum (pressure<10 ^-6Millibar) prepares bilayer cells (battery of double-layer structure) and body heterojunction battery (BHJ battery) down.

Bilayer cells (ITO/ indanthrene compound/C ₆₀/ Bphen/Ag):

Said bilayer cells is passed through indanthrene compound and C ₆₀Be deposited on successively on the ITO substrate and prepare.Two-layer deposition rate is 0.1nm/ second.The evaporating temperature of said indanthrene compound sees table 1.

Table 1

The indanthrene compound	Evaporating temperature [° C]
		Indanthrene blue	330
Deuterate indanthrene blue (embodiment 1)	200
		N, N '-diphenyl indanthrene (embodiment 2)	240

The indanthrene compound	Evaporating temperature [° C]
		N, N '-dimethyl indanthrene (embodiment 3)	200

At 410 ° of C deposit C ₆₀In case apply Bphen layer (layer thickness is 6nm), apply the thick Ag layer of 100nm as top electrode through vapour deposition at last.The area of this battery is 0.031cm ²BHJ battery (ITO/ (indanthrene compound: C ₆₀-weight ratio is 1:1)/C ₆₀/ Bphen/Ag):

In order to prepare BHJ battery (body heterojunction battery), with indanthrene compound and C ₆₀Coevaporation also is applied on the ITO with the same deposition speed of 0.1nm/ second, thereby makes that the weight ratio in the mixed active layer is 1:1.Bphen and Ag layer are through applying the described vapour deposition process of bilayer cells.As far as BPhen, layer thickness is 6nm, and as far as Ag, layer thickness is 100nm.

Test:

Used solar simulator is AM 1.5 simulators with xenon lamp (model 16S-150V3) available from Solar Light Co.Inc..Filtration is lower than the UV scope of 415nm and under environmental condition, measures current-voltage.The intensity of said solar simulator is proofreaied and correct with monocrystalline FZ solar cell (Fraunhofer ISE), and the measurement deviation factor is about 1.0.

The result:

Bilayer cells:

The BHJ battery:

η efficient

The FF fill factor, curve factor

I _ScShort circuit current

V _OcOpen circuit voltage

The battery that comprises C60 and indanthrene compd A, B, C and D combination has high open circuit voltage.When with the combination of fullerene compound such as C60, because its long wave absorbs said indanthrene compound and is particularly useful in the laminated cell.

Claims

1. organic solar batteries that comprises at least one photosensitive area, said photosensitive area comprises the indanthrene compound that at least a and at least a fullerene compound contacts, and wherein said indanthrene compound is selected from the compound of general formula (I):

Wherein

R ¹-R ¹²Group is selected from hydrogen, halogen, nitro, cyanic acid, hydroxyl, carboxyl, carboxylic acidulants base, SO independently of one another ₃H, azochlorosulfonate acid compound base, Ne ^aE ^bAnd be selected from each case and do not replace or substituted alkyl, alkoxyl, alkylthio group, cycloalkyl, aryl, aryloxy group, arylthio, heteroaryl, heteroaryloxy, heteroarylthio, oligomeric (mixing) aryl, oligomeric (mixing) aryloxy group and oligomeric (mixing) alkylthio group, wherein E ^aAnd E ^bBe hydrogen, alkyl, cycloalkyl or aryl independently of one another.

2. according to the solar cell of claim 1, it is the assembly battery forms of laminated cell.

3. according to the organic solar batteries of claim 1, wherein in the compound of general formula (I), R ^aAnd R ^bGroup is selected from hydrogen, deuterium, C independently of one another ₁-C ₁₂Alkyl, C ₇-C ₂₂Aralkyl, C ₄-C ₇Cycloalkyl, C ₆-C ₁₀Aryl and C ₇-C ₂₂Alkaryl.

4. according to each organic solar batteries in the aforementioned claim, wherein in the compound of general formula (I), R ^aAnd R ^bThe two is hydrogen or the two is deuterium or the two is C group ₁-C ₆Alkyl or the two are phenyl or the two is C ₁-C ₁₂Alkyl phenyl or the two are naphthyl.

5. according to each organic solar batteries in the aforementioned claim, wherein in the compound of general formula (I), R ¹-R ¹²Group is selected from hydrogen, F, Cl, hydroxyl, C independently of one another ₁-C ₁₈Alkyl, C ₁-C ₁₂Alkoxyl, C ₁-C ₆Alkylthio group, C ₇-C ₂₂Aralkyl, C ₇-C ₂₂Aralkoxy, C ₇-C ₂₂Aromatic alkylthio, C ₄-C ₇Cycloalkyl, C ₆-C ₁₀Aryl, C ₇-C ₂₂Alkaryl, C ₇-C ₂₂Aryloxy alkyl, C ₇-C ₂₂Alkane arylthio, amino, list (C ₁-C ₁₂Alkyl) amino, two (C ₁-C ₁₂Alkyl) amino, NH (C ₆-C ₁₀Aryl), N (C ₆-C ₁₀Aryl) ₂, heteroaryl and oligomeric heteroaryl, wherein the heteroaryl of heteroaryl and oligomeric heteroaryl can not be substituted independently of one another or is selected from C by 1,2,3 or 4 ₁-C ₁₂Alkyl and C ₁-C ₁₂The group of alkoxyl replaces.

6. according to each organic solar batteries in the aforementioned claim, wherein in the compound of general formula (I), R ¹-R ¹²Group is selected from hydrogen, C independently of one another ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkoxyl, phenyl, naphthyl, phenoxy group, naphthoxy and oligomeric thio-phenyl, wherein phenyl, naphthyl, phenoxy group, naphthoxy and oligomeric thio-phenyl are not substituted or have 1 or 2 and be selected from C ₁-C ₁₂Alkyl and C ₁-C ₁₂The substituting group of alkoxyl.

7. according to each organic solar batteries in the aforementioned claim, wherein in the compound of general formula (I), 0,1,2,3 or 4 R ¹-R ¹²Group has the definition that is different from hydrogen.

8. according to each organic solar batteries in the aforementioned claim, wherein said indanthrene compound is for being selected from the compound of general formula (I.1):

Wherein

9. according to each organic solar batteries in the aforementioned claim, wherein said photosensitive area comprises at least a fullerene and/or the fullerene derivate as the fullerene compound.

10. organic solar batteries according to Claim 8, wherein said photosensitive area comprises as the C60 of fullerene compound or [6,6]-phenyl-C61-methyl butyrate.

11., wherein exist at least one to be the photosensitive donor-receiver transition region of body heterojunction form according to each organic solar batteries in the aforementioned claim.

12. according to the purposes as electron donor in organic photovoltaic devices of each defined general formula (I) compound among the claim 1-7.

13. according to the purposes as light-sensitive material in organic solar batteries of each defined general formula (I) compound among the claim 1-7.

14. according to the purposes of claim 13, it is used for comprising at least one solar cell that comprises at least a photosensitive area according to each defined general formula (I) compound of claim 1-7 and at least a fullerene compound.

15. according to the purposes of claim 14, wherein used fullerene compound is C60 or [6,6]-phenyl-C61-methyl butyrate.

16. each purposes is used for laminated cell among the claim 12-15.

17. the compound of a following formula:

18. the compound of a formula I:

Wherein

R ¹And R ⁹The two is phenoxy group, and R ^a, R ^b, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ¹⁰, R ¹¹And R ¹²Group all is a hydrogen; Perhaps

R ⁵And R ⁸The two is methoxy, and R ^a, R ^b, R ¹, R ², R ³, R ⁴, R ⁶, R ⁷, R ⁹, R ¹⁰, R ¹¹And R ¹²Group all is a hydrogen.